National Science Review

REVIEW 2: 167–182, 2015

doi: 10.1093/nsr/nwv019
Advance access publication 24 April 2015

CHEMISTRY

Special Topic: Catalysis—Facing the Future

Applied catalysis for sustainable development of chemical
industry in China
Zaiku Xie1,∗ , Zhicheng Liu2 , Yangdong Wang2 and Zhonghao Jin2

ABSTRACT
Progressing green chemical technologies is significant to the sustainable development of chemical industry
in China, as the energy and environment problems increasingly became great challenges to the whole
society. The scientific connotation of sustainable energy chemical engineering can be generalized as green
carbon/hydrogen science which means optimization of carbon/hydrogen atom economics based on high
efficient catalysis and low-carbon emission. This review illustrated recent advances in developing
sustainable technologies for applied catalysis in chemical industry of China, including the fields of high
efficient conversion of heavy oil, green petrochemical catalytic technologies, clean utilization of coal and
natural gas, promoting sustainable resources and clean energy, etc. Moreover, from the view of industrial
point, some important common scientific problems were discussed and summarized, such as the relation
between molecular diffusion and catalyzing efficiency, homogeneous catalysis in heterogeneous catalysts,
in situ or operando characterization of industrial catalysis, etc., aiming to supplying a forward roadmap to
academia and/or industry.
Keywords: applied catalysis, catalytic efficiency, green carbon/hydrogen science, green petrochemical
technology, coal chemical technology, biomass energy technology

1 China Petroleum &

INTRODUCTION processes. It is known that the efficient utilization
Chemical Corporation, At present, there are many challenges on sustain- of carbon/hydrogen resources and carbon recycling
Beijing 100728, China able development of energy chemical industry in are of great importance for the sustainable develop-
and 2 Sinopec China, including inferior energy structure, shortage ment of chemical industry, and there are many re-
Shanghai Research of high-quality resources such as oil and natural gas, lated challenging scientific issues to be solved. A sim-
Institute of low-energy consuming efficiency and severe envi- plistic carbon cycle relating the utilization of fossil
Petrochemical ronmental pollution, etc. Therefore, the efforts de- resources, the conversion of biomass and the recy-
Technology, Shanghai
voted to green technique, low-carbon emission and cling of CO2 is shown in Fig. 1. Actually, however,
201208, China
improving resource utilization efficiency have be- the real carbon cycle has not achieved because effi-
come a current social consensus, which is also de- ciencies of most steps in the scheme were still low,
∗ Corresponding
sired for sustainable development of the energy and leading to the tremendous net emission of CO2 to
author. E-mail: chemical industry. the environment. Therefore, devoting to realizing
xzk@sinopec.com
Since the concept of green chemistry proposed in entire carbon cycle, He et al. [3,4] recently put for-
the early 1990s, it has received extensive attention ward the concept of green carbon science, which was
Received 1 February and become firmly entrenched both in academia defined as the study and optimization of the trans-
2015; Revised 1 April and industry during recent two decades [1,2]. The formation of carbon-containing compounds in rel-
2015; Accepted 3 general principles of green chemistry guide the evant processes, involving in the entire carbon cy-
April 2015
design of environmentally benign products and cle from carbon resource processing, carbon energy


C The Author(s) 2015. Published by Oxford University Press on behalf of China Science Publishing & Media Ltd. All rights reserved. For Permissions, please email:

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 168 Natl Sci Rev, 2015, Vol. 2, No. 2
CO2
Fuel burning
Chemical
transformation Photosynthesis
Fuel, Chemicals
Processing
Coal, Oil, Natural gas Biomass
Figure 1. The simplified carbon cycle and related processes
for green carbon science. Adapted from [4] C 2013 Wiley-
VCH Verlag GmbH & Co. KGaA, Weinheim.
utilization, CO2 fixation and carbon recycling to
utilize carbon resources efficiently and minimize
net CO2 emission. On the latest 485th Xiangshan-
Science conferences 2014, this concept was further
discussed as one of theme reports, coupling with
concept of green hydrogen science [5] which refers
to the low-carbon production of hydrogen, as well as
its highly efficient storage, etc.
Five main feasible ways can be summarized as
follows for implementation of sustainable develop-
ment of chemical industry: (1) developing higher
efficient catalytic technologies for petroleum
processing and petrochemical industry, including
higher efficient catalytic materials, process coupling,
combination and intensification; (2) developing
green processes with higher atom economy and
low emission or pollution; (3) developing catalytic
technologies based on diversification of raw ma-
terials other than oil; (4) developing technologies
of carbon capture, utilization and storage (CCUS)
and solar energy conversion technologies; (5)
developing technologies for green energies, such
as low-carbon hydrogen production and highly
efficient storage of hydrogen.
Since most of the processes in energy chemical
industry involving catalysis process, it is a key issue
on developing catalysis science and technology to
achieve the goal of efficient utilization of resources
and green production. Herein, we will review recent
progress on applied catalysis for sustainable develop-
ment of chemical industry in China, including five
main aspects such as the high efficient utilization
of oil resources, green petrochemical catalytic pro-
cesses, coal chemical catalysis technologies, catalysis
on syngas and natural gas resources and catalysis on
renewable, clean energy and carbon dioxide utiliza-
tion, and so on.
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REVIEW
RECENT PROGRESS IN APPLIED
CATALYSIS ON GREEN CHEMICAL
INDUSTRY IN CHINA
Catalysis on high efficient utilization
of oil resources
Refinery catalytic technology needs continuous up-
grading and innovation, with the trends of increas-
ingly heavier crude oil resources and desires of
cleaner fuel products. Besides, lots of measures on
refining and green products have been taken, such
as new desulfurization and denitration techniques to
meet the demands of oil products of high quality.
There are two important methods in converting
heavy oil into light fuel and diesel, fluid catalytic
cracking (FCC) and residue fluid catalytic cracking
(RFCC) followed with hydrocracking processes [6].
As for FCC or RFCC technologies, the main chal-
lenge is to improve the catalytic conversion of heavy
oil and maximize light oil production. Recently,
Zhou et al. synthesized a Nest Shape Y zeolite (called
NSY) with hierarchical porosity by in situ growth of
NaY zeolites on grains of Kaolin clay [7]. This NSY
zeolite catalyst has higher gasoline production and
lower diesel production than the conventional ones.
Shen et al. synthesized a kind of mesoporous ZSM-
5 by desilication with base treatment. They found
that more yield of light olefins could be obtained in
catalyzing heavy oil from Daqing oil field [8]. Bao
et al. reported the synthesis of Kaolin/NaY/MCM-
41 composite [9], by which higher yield of gaso-
line and diesel oil, and lower tail gas and coke than
conventional catalysts were found in the catalytic
conversion of heavy oil, because of the obvious im-
provement of hierarchical porosity. It is worth not-
ing that better catalytic performances of all of the
above-mentioned catalysts should mostly attribute
to their richer porosity than that of conventional cat-
alysts.
Except for developing hierarchical porous struc-
ture, employing larger microporous zeolites as addi-
tives in catalysts may be another choice to improve
the catalytic performance. As shown in Fig. 2, we
can find more and more zeolitic with larger micro-
pores have been employed as additives in the FCC
catalysts [10]. In a word, developing applicable FCC
catalysts should pay close attention to hierarchical
zeolites and/or larger microporous zeolites in the
future.
In the field of hydrocracking of heavy oil, Zong
et al. have carried out systematic researches aim-
ing to high efficient utilization of carbon resources.
Based on the analysis of heavy oil on molecular
level, they invented novel hydroprocessing cata-
lysts on selective hydrogenation of polycyclic aro-
matic hydrocarbons (PAHs), developed slurry bed
 REVIEW
Industrial used
Being developed
Zeolitic additives
for FCC catalysts
Pore size
MCM-41
VPI-5
USY, REUSY
SAP0-5
REY, HY
Zeolite β Mordenite
ZSM-5 MCM-22
Gasoline cracking/ VGO cracking/ Residue cracking
Figure 2. Trend on pore sizes of zeolitic additives for FCC
catalysts. Reproduced with author’s permission from [10].
hydrocracking technologies, performed coupling
and intensification of catalytic distillation and sep-
aration processes, and integrated coupling of heavy
oil cracking with biological refining process of micro
algae and CO2 CCUS [11–13]. Moreover, basic sci-
entific problems on colloid stability control, hydro-
dynamic and mass transfer characteristics of slurry
bed reactor etc. have also been studied.
In the area of desulfurization of gasoline, applica-
tion of S-Zorb technology is a big advance to be men-
tioned, which was first developed by Conoco Phillips
Company and then became an acquisition technol-
ogy of Sinopec including a new generation of special
adsorbent and fluidized bed process [14]. This spe-
cial adsorbent is composed of zinc oxide, nickel ox-
ide and silica–alumina. By S-Zorb technology, sulfur
can be transferred from oil molecules onto the adsor-
bent and the remaining hydrocarbon fragments can
be released out. Because sulfur components are re-
moved in time, chemical equilibrium will continue
moving to desulfurization side, which would result
in yield of fuel oil high to 99.5%. Therefore, S-Zorb
technology by adsorption-desulfurization method
can achieve deeper desulfurization than traditional
hydrodesulfurization technologies [15]. And after
the adsorption and catalytic process, the adsorbent
or catalyst can be regenerated under enriched oxy-
gen environment in the reactor. Moreover, it takes
other advantages such as lower loss of octane num-
ber (less than 1%), lower consumption of hydro-
gen and energy, lower requirement on purity of hy-
drogen, and so on [16]. The products by this tech-
nology can reach the National IV and V standard
for gasoline of which S content is less than 50 and
10 ppm, respectively. By the way, there are other new
catalytic technologies developed for hydrodesulfur-
ization of gasoline, e.g. Li et al. has successfully devel-
oped a fixed-bed catalytic technology for ultradeep
desulfurization of gasoline, which would possess ad-
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Xie et al. 169
vantages for easier operation and regeneration pro-
cedure, as well as lower operation cost [17].
Then, with the increase of processing capacity of
FCC units and more heavy oil components in the
feedstock, large amount of low-quality diesel distil-
lates, especially the light cycle oil (LCO) has been
produced. Since it has high sulfur, nitrogen and aro-
matic content, low cetane number and poor sta-
bility, it needs further processing such as by hy-
drofining or hydroupgrading processes to maximize
the diesel production [18]. In recent years, MCI
technology, a novel hydrotreating process for up-
grading low-quality diesel distillates, has been suc-
cessfully developed by Fang et al. This process can
perform hydrotreating reactions (HDS and HDN),
which would greatly improve cetane number of
diesel product under nearly the same operating con-
ditions of hydrotreating process [19,20]. On the
other hand, maximizing the production of BTX aro-
matics is another feasible way of processing LCO,
which includes three main steps, hydrofining, selec-
tive hydrogenation cracking and transformation of
middle distillate. Nie et al. referred that one of the
difficulties for this way was the selectively hydroc-
racking of PAHs i.e. tetralin, of which optimizing the
coordination of acid sites and metal sites on cata-
lysts, as well as reducing the distance between this
two sites could be a potential approach to further
promote the reaction activity and to improve objec-
tive product selectivity [21]. Zheng et al. also carried
out some studies and got some positive results on se-
lective catalytic conversion of PAHs components in
LCO to BTX aromatics [22].
Besides, alkylate gasoline, which is an important
component of reformulated gasoline with high oc-
tane number, has received the widespread attention
in recent years. Alkylate gasoline can be produced
by alkylation of isobutane with butane from refinery
by-products. However, current alkylation processes
use concentrated sulfuric acid or hydrofluoric acid
as catalysts, which would inevitably bring equipment
corrosion and environment pollution. Chemists are
looking for environmental friendly alternatives in-
stead of the conventional catalysts. Recently, ionic
liquid-catalyzed alkylation has aroused much atten-
tion because of their clean catalytic properties in
alkylation processes. However, common acidic ionic
liquids such as aluminum chloride acid ionic liq-
uids have a lower selectivity of alkylate gasoline than
conventional liquid acids [23]. Xu et al. found that
the selectivity of alkylate gasoline can be improved
by adding certain metal chlorides to the aluminum
chloride-based ionic liquids [24]. The main chal-
lenge is the miscibility and stability of the added
components in the ionic liquids. Therefore, they in-
vented a novel multicenter composite ionic liquid,
 170 Natl Sci Rev, 2015, Vol. 2, No. 2
Table 1. Three generations of green production technologies of caprolactam developed by Sinopec. Adapted from [27] C
2013 Science China Press.
Reaction processes The 1st generation of technology
Ammonium oxidation reaction:
4NH3 + 7O2 4NO2 + 6H2O
Hydroxylamine reaction:
2NO2 + 2H+ + 5H2 2NH3OH+ + 2H2O
Ammoximation Oximation reaction:
O NOH
reaction
NH3OH3 + + + H2O + H+
Ammonium decomposition reaction:
2NH4+ + NO + NO2 2N2 + 2H+ + 3H2O
NOH O
Rearrangement
HN
reaction + 1.5H2SO4 + 3NH3
Purification
Raney-Ni catalyst with tank reactor
reaction
[Et3 NH]+ [AlCuCl5 ]− , which presented high selec-
tivity of favorable products, long life of catalysts, and
importantly without any problem of self-phase sep-
aration aroused from miscibility [25,26]. Based on
such new ionic liquids catalyst and alkylation pro-
cess, a 100 kt/a scale industrial plant has been built
up recently.
Catalysis on green petrochemical
processes
It is known that basic organic raw materials such
as olefins, aromatics and organic monomers con-
taining oxygen/nitrogen elements are mainly pro-
duced from petrochemical industry. However, many
current petrochemical processes still suffered from
high-energy consumption and/or large amount of
wastes or pollutions. Sustainability in petrochemical
industry is desired all over the world, which is es-
pecially significant in China, encouraging more re-
searchers to develop innovative technologies on en-
ergy saving, green processes, environmental safety,
etc.
One typical example is the green production pro-
cess of caprolactam developed by Sinopec, which
consisted of three main innovations (Table 1) [27].
For the oximation process of cyclohexanone, the
traditional process contains four steps: ammoxida-
tion, hydroxylamine, oximation and ammonium de-
composition, while only one step was needed in
new green process by TS-1 zeolite catalyst. Unfor-
tunately, conventional TS-1 zeolite catalyst cannot
reach the conversion and stability requirement in in-
dustry. Lin et al. invented a new hollow structured
TS-1 zeolite (called HTS) by using a so-called mul-
tistage crystallization method [28] which exhibited
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The 2nd generation of technology The 3rd generation of technology
O NOH
HTS
+ NH3 + H2O2 + 2H2O The same as 2nd generation
NOH
+ 1.5(NH4)2SO4 Silica zeolite NH
The same as 1st generation
O
New process
Amorphous Ni alloy integration with
The same as 2nd generation
magnetically stabilized bed reactor
higher conversion and stability than conventional
TS-1 zeolite catalyst. The second innovation is on
the rearrangement process of cyclohexanone oxime.
By employing radial flow moving-bed reactor as well
as zeolite catalyst consisted of pure silica, a gas-phase
Beckmann rearrangement process has been devel-
oped in absence of ammonia sulfate, in advantage of
environmental benign and low cost. The third inno-
vation is on the purification process of caprolactam.
Amorphous Ni alloy integrated with magnetically
stabilized bed reactor has been used to dramatically
improve the efficiency of hydrogenation and catal-
ysis utilization. Based on the commercial applica-
tion results, the investment of caprolactam produc-
tion plant decreased 70%, 10% operation costs was
saved and atom utilization rate increased from 60
to 90%, respectively, and more importantly, waste-
free was realized. Since green caprolactam produc-
tion technology practiced green chemistry concepts
and gained great economic and social benefits, it can
be considered as a successful example of green chem-
istry.
Selective oxidation is another important subject
in green chemical technologies. Among them, new
green technologies of olefin epoxidation have at-
tracted great attention for recent decades. One of the
green and efficient routes for preparation of propy-
lene oxide (PO) is hydrogen peroxide-propylene ox-
ide (HPPO) process with hydrogen peroxide as ox-
idant and titanium silicates as catalytic materials. A
HPPO technology based on a new titanium silicate
catalyst called HTS has been developed by Sinopec
[29]. Pilot test has been carried on for more than
4000 h, approving excellent stability of the catalyst
[30].
Employing cumene hydroperoxide (CHP) so-
lution as oxidation regent, another route for PO
 REVIEW Xie et al. 171

production was developed by Jin et al. in China. The Catalysis on coal-based methanol
reported Ti/HMS catalysts possessed typical meso- conversion technologies
porous structure and tetracoordinated Ti species in
For the sustainable development of energy chemi-
the framework [31]. After treating with silane, they
cal industry, catalytic technologies based on diver-
found that the hydrophobicity of Ti/HMS was ob-
sification of raw materials other than oil should at-
viously improved, leading to excellent catalytic ac-
tract more and more attentions. Since coal is one
tivity and stability and PO selectivity. Pilot test as
of the main energy resources in China, it is a good
long as 2400 h showed the high CHP conversion
choice to develop chemical industry involving coal
over 99.0% and the selectivity of PO as high as 97.0%
conversion as important supplement to the petro-
[32]. Of course, there are other potential routes for
chemical industry. For example, by methanol-to-
green technologies of olefin epoxidation, for exam-
olefins (MTO) or methanol-to-propylene (MTP)
ple, Xi et al. ever reported a novel heteropolyphos-
process, methanol can be converted into ethylene,
phatotungstate catalysts which performed special re-
propylene and other light olefins which correlated
action controlled phase transfer function [33] and
petrochemical with coal chemical industry. Now in
can be coupled with direct production of hydrogen
China, MTO technique has been successfully indus-
peroxide by ethyl-anthraquinone/ethyl-anthracene
trialized by Dalian Institute of Chemical Physics of
hydroquinone method. New processes based on this
Chinese Academy of Sciences (DICP) and Sinopec
special catalyst are under development, such as in the
Shanghai Research Institute of Petrochemical Tech-
production of propylene epoxide and epoxy chloro-
nology (Sinopec SRIPT), successively. One of the
propane [34] which will be discussed in the follow-
main challenges in MTO or MTP is how to maxi-
ing section.
mize the yield of light olefins and prolong the life-
There is another example on green technology
time of catalyst. A great deal of research about cat-
which involves in the production of monoethy-
alytic materials, reaction mechanism as well as chem-
lene glycol (MEG) by catalytic hydration of ethy-
ical process has been carried out in the last years.
lene oxide (EO). Many heterogeneous catalysts with
Many mechanism studies have demonstrated
ion-exchanged resin (IER) immobilized with qua-
that the reaction of methanol conversion to light
ternary phosphonium halides, polymeric organosi-
olefins is controlled by molecular diffusion and pos-
lane ammonium salt and macrocyclic chelating com-
sesses a complex hydrocarbon pools mechanism.
pounds, have been studied to reduce energy con-
Liu et al. developed the DMTO process which was
sumption. However, the major challenge is stabil-
based on SAPO-34 zeolite catalysts and fluidized
ity of catalyst, because of the easy swelling of resins
bed reactor [37]. They first observed the existence
under reaction conditions. He et al. has designed
of hepta MB+/HMMC in the MTO process by us-
resin/carbon nanotuble (CNT) composite catalyst
ing extra large cage of novel molecular sieve mate-
to overcome this problem [35]. Adding CNT into
rial, DNL-6 [38], which confirmed the rationality
resin could greatly enhance thermo stability and
of hydrocarbon pools mechanism. In addition, 13 C
anti-swelling capability during the reaction of hydra-
isotope tracer experiments further verified the im-
tion of EO. It was found that the glass transition tem-
portant role of the intermediate in the conversion of
perature (Tg) of this composite catalyst increased
methanol and the formation pathway of light olefins
from 125 to 132◦ C. And the swelling quality of the
from carbon cation intermediate (Fig. 3).
composite could be reduced to almost half of PS-
DVB. Furthermore, the normal reaction tempera-
ture of hydration of EO can be increased from 60 to
100◦ C. The enhanced thermal stability of the poly-
mer composite facilitated the reaction operation at
higher temperature, leading to reduction of the feed- Ethene product H2O
stock/water ratio to almost half (from 20–25 to less 13
13
CH3OH
CH3OH H 2O
than 12), and greatly cutting down the energy con-
sumption in the whole process. The obtained poly- Z-H Z-H
Propene product
mer/MWNTs composite performed very well in the
H213C 13
CH2
life test of catalytic hydration of EO, in which there
was no obvious decline in conversion or selectiv- 13
H2O CH3OH
ity after 2200 h. Very recently, they reported a kind Z-H
of graphene-reinforced nanocomposite IERs which
also exhibited excellent anti-swelling property, ther- Figure 3. Methylbenzenes carbenium ions as intermediates
mal stability of the materials and good catalytic and the likely path for olefin generation. Adapted from [38]
performances [36]. 
C 2012 American Chemical Society.

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 172 Natl Sci Rev, 2015, Vol. 2, No. 2
H2O
HO
OH OH
HO
H2O H2O
OH
HO
H2O
H2O OH
H2O
H2O OH
Framework of zeolite
Figure 4. Reaction network of the MTO conversion in acidic zeolites based on olefin derived carbenium ions intermediates
mechanism. Adapted from [44] C 2013 Elsevier Inc.
Xie et al. has carried out systematic studies on cat-
alytic technologies of methanol conversion to light
olefins and aromatics for many years. They have pre-
pared a low wear industrial fluidized MTO catalyst
with high yield of olefins by adjusting acidity, crys-
tal morphology and multiscale porosity of SAPO-
34 zeolite [39–41]. And a new chemical process in-
cluding the fast fluidized bed reaction-regeneration
technology has also been developed into applica-
tion. In addition, they have conducted molecular
simulation studies on reaction mechanism of hydro-
carbon pools. Except for the side-chain and paring
mechanism based on methylbenzenes carbenium
ions intermediates [42,43], they put forward a new
mechanism involving the olefin-derived carbenium
ions intermediates (Fig. 4) [44]. Furthermore, they
are also developing zeolitic catalyst for MTP process.
By adjusting porosity, crystal morphology and sizes,
they have successfully prepared a kind of full crys-
talline hierarchical zeolite catalyst with better diffu-
sion and higher catalytic performance than conven-
tional catalysts [45]. It is reported that the life of
the catalyst has exceeded 2000 h. The MTP pilot
test with 5 kt/a scale has already been completed
recently.
Methanol can also be directly converted to aro-
matics (MTA technology). Recently, Wei et al. has
developed a Zn/Ag-modified ZSM-5 catalyst [46],
and realized a continuous reaction-regeneration
process by integrating fluidized bed of aromatization
with the catalyst regeneration process, and control-
ling the amount of coke on catalysts in aromatiza-
tion reactor [47]. A pilot test with 10 kt/a showed
that the single-pass yield of aromatics arrived at
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REVIEW
Carbenium ions
OH (Cn+1+)
Methylation
CH3OH
Alkenes
H2O
Deprotonation
Isomerization
Alkoxides Carbenium ions
(CnZ) (Cn+)
Cracking
Alkoxides + Alkenes
Deprotonation
OH Hydride transfer
Alkenes Alkenes + Dienes
Cyclization
Hydride transfer
Aromatics
55∼65% and the total yield of aromatics reached
about 80%.
Alkylation of toluene with methanol to xylene
(MTX) technology has been successfully devel-
oped by Sinopec SRIPT, which employed a kind of
nanozeolite catalyst [48,49] and a new MTX cat-
alytic process [50,51]. It has been reported that the
world’s first industrial plant with 200 kt/a scale was
run up at 2013, in which the lifetime of catalyst ex-
ceeded 3 months with the conversion of toluene and
methanol to 30 and 100%, respectively, and the se-
lectivity of xylene reaching up to 70%. On the other
hand, Liu et al. from DICP has developed a fluidized
bed catalyst to solve the fast deactivation problem of
zeolite catalysts [52], and a pilot test had been taken
on a fluidized bed reactor.
Catalysis of syngas and natural gas
resources
Fischer–Tropsch synthesis (FTS) is a key technol-
ogy for converting the syngas derived from non-
petroleum carbon resources, such as coal and nat-
ural gas, into valuable fuels and chemicals ranging
from C1 to C120 . Since then, FTS has revived great
interest of many researchers. High-performance cat-
alyst, reactor, procedure and their optimal integra-
tion are the most important features of a high-
performance FTS process. Recently, combined with
the theory calculation, process simulation and ex-
perimental studies, Li and co-workers investigated
the structure and its transition of iron-based cat-
alyst in the process of FTS [53]. Especially by
identifying the effects of CO pretreatment and K
 REVIEW
(a) (b)
(111)-1.75
(211) (133)-1.75
(310)
(113)-2.00
(100) (110)
(100)-2.00
(011)-2.20
)
(131)-2.00
11
(1
(001)-2.00
(010)-1.25
K/Fe = 0 K/Fe = 1/12
Figure 5. (a) Potassium promoter (K2 O) modifies the crystallographic orientation in catalysts. Adapted from [54] C 2011 Wiley-VCH Verlag GmbH & Co.
KGaA, Weinheim. (b) Morphology of χ -Fe5 C2 investigated under CO and H2 /CO pretreatment. Adapted from [53] C 2012 Elsevier Inc.
promoter [54] on the surface structure of FexCy
active phase and catalytic performance [55], a new
perspective for understanding the CO dissociation,
CH4 formation and chain growth was received, as
shown in Fig. 5. Additionally, an inherent relation-
ship between the preparation method and reaction
conditions-catalyst structure-catalytic performance
has also been revealed [56]. Based on these research
findings, a unique FTS catalyst and complete tech-
nological process for high-temperature slurry phase
reactor has been developed [57–59], which has been
successfully practiced at industrial scale for 100 kt/a.
This innovative FTS process effectively achieved a
heat balance and improved the energy utilization ef-
ficiency of whole system due to the coproduction of
high-grade steam and power generation by raising of
the reaction temperature from 200–250◦ C to 260–
290◦ C.
There are still some scientific challenges in the
research area of FTS, among which the selectivity
control is one of the most attractive and diffi-
cult challenges. Over conventional FT catalysts,
the hydrocarbon products generally follow the
Anderson–Schulz–Flory (ASF) distribution, owing
to a polymerization model of the chain growth pro-
cess. The ASF distribution of FTS imposes a limit
to the maximum selectivity of 45 and 30% attain-
able for gasoline-range and diesel-range products,
respectively. Moreover, the yield of CH4 and
heavy hydrocarbons are usually significantly
higher than that predicted by the ASF distribu-
tion. Therefore, the development of novel FTS
catalyst for optimizing the product distribution
and improving the selectivity for gasoline-range
and diesel-range products has acquired more and
more attentions. Recently, Wang et al. reported
an encouraging progress to overcome the ASF
distribution by employing bifunctional FTS catalyst
based on zeolite and metals [60]. During the
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Xie et al. 173
χ-Fe5C2
(111)-2.17
Pretreatment
(133)-1.75
(113)-2.00
(100)-2.25
(011)-2.40
(131)-2.20
(001)-2.50
(010)-2.50
(110)-2.40
CO-600K,1 atm Syngas-600K,1 atm, H2/CO=4/1
FTS process over these catalysts, FTS products cat-
alyzed by the active metal (i.e. cobalt) phase are hy-
drocarbons with wide distribution and then the acid
sites in zeolites can catalyze the secondary conver-
sions of these heavy hydrocarbons, such as hydroc-
racking and isomerization. Employing the designed
Ru/meso-ZSM-5 composite as catalyst, the selectiv-
ity of CH4 decreased to about 5%, while the selectiv-
ity for C5–C11 increased to about 81% with a ratio
of isoparaffins to n-paraffins of about 2.7, indicating
the significantly higher selectivity for gasoline-range
products than the ASF distribution (maximum ca.
45%). Furthermore, a high selectivity for C10 –C20 to
reach about 60–65% was found over Ru/CNT [61].
With the rise of coal chemical industry, tech-
niques of ethylene glycol (EG) production with syn-
gas that derived from coal or natural gas have drawn
much attention. Compared with traditional route via
vapor phase oxidation of ethylene into epoxide and
followed by consequent hydration, better atom eco-
nomic value can be achieved by the syngas route.
In recent years, a research team from Fujian Insti-
tute of Research on the Structure of Matter, Chi-
nese Academy of Sciences has developed a series
of Cu-Cr supported catalysts for the vapor phase
catalytic synthesis of oxalate ester and the corre-
sponding process flow, and investigation on the NO
production has also been carried out [62,63]. The
process of vapor phase catalytic synthesis of oxalate
ester by CO and hydrogenation of dimethyl oxalate
into EG has been fully tested in a pilot plant with
a capacity of 300 t/a demo plant with a capacity
of 10 kt/a in succession. Moreover, an industrial
scale plants with 200 kt/a capacity has been built
in Tongliao, Inner Mongolia [64]. There are also
other accessible reports about this technology, for
example, an oxidative dehydrogenation catalyst with
low noble metal content for the CO refining and
a coupling catalyst of CO and methyl nitrite into
 174 Natl Sci Rev, 2015, Vol. 2, No. 2
(a) (b)
Products selectivity (%)
Figure 6. High efficient catalyst with single iron sites embedded in a silica matrix for direct, non-oxidative conversion of methane to ethylene, aromatics,
and hydrogen. Adapted from [67] C 2014 American Association for the Advancement of Science.
dimethyl oxalate (DMO) has developed by Sinopec
SRIPT [65], by combining the CO coupling and NO
oxidative esterification. A pilot plant with a capac-
ity of 1000 t/a has been completed by this process,
with the CO single-pass conversion to more than
80% and the selectivity of DMO reaches more than
99%. Then an industrial scale plants with 200 kt/a ca-
pacity has been built in succession. It is also reported
that a team from Tianjin university had completed a
pilot plant with a capacity of 200 t/a recently [66].
Besides, Zhao et al. recently reported a Pd catalyst
supported by nanocarbon fiber which showed high
catalytic performance with the methyl nitrite single-
pass conversion of more than 85% and the selectivity
of EG close to 100%, indicating an alternative route
on the choice of catalyst support [66]. In a word,
massive research studies and many pilot tests have
been made on the vapor phase synthesis of oxalate
ester in recent years, which indicates that this tech-
nology becomes more and more mature in China. In
the future, more attentions will be paid on the opti-
mum of process flow and the NO cyclic utilization,
etc.
In the conversion of natural gas resources, con-
verting natural gas to high-valued chemicals and
liquid fuels through C1 chemistry is a challenge
to catalysis science. Currently, indirect route is the
method used widely in the conversion of methane.
Methane is firstly transformed into syngas by re-
forming with H2 O, O2 and CO2 ; then the syngas
was converted into higher hydrocarbons or lower
olefins by corresponding chemical routes, such as
FTS and MTO. Unfortunately, these multistep pro-
cesses usually exhibited low efficiency, high costs
and enormous CO2 emission. Reversely, the direct
route is a promising method in term of possessing
simple process flow, low-energy consumption and
CO2 emission. To achieve the direct conversion of
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100 25
90 Ethylene
Methane conversion (%)
Ethane
80 20
Benzene
70 Naphthalene
Coke
60 15
50
40 10
30
20 5
10
0 0
Blank 0.5Fe/ZSM 0.5Fe/SiO2 0.8Fe/SiO2 0.5Fe SiO2 0.2Fe/SiC
Catalysts
CH4 efficiently, the challenges lie in cleaving of
the first C–H bond, while suppressing further cat-
alytic dehydrogenation, and avoiding both CO2
generation and coke deposition, which initiated a
worldwide research surge to explore the selective
activation and orient transition of methane. Very
recently, Bao et al. have made a significant progress
on the direct conversion of methane, in which car-
bon atom efficiency is close to 100% [67]. They
found that the synthesized single iron sites embed-
ded in a silica matrix enable direct, non-oxidative
conversion of methane, exclusively to ethylene and
aromatics (benzene and naphthalene) via initiating
methyl radicals and a series of vapor phase reactions
under high temperature (Fig. 6). This finding antici-
pated that the direct conversion of methane is possi-
ble to be commercialized based on the development
of catalysis science.
Catalysis on renewable, clean energy
and carbon dioxide utilization
As the rapid decrease of fossil fuel reservoir, the uti-
lization of renewable feedstock attracts more and
more attentions in recent years. It is expected that
the industrialization of some emerging biomass en-
ergy technology will be achieved in the next 10 or
20 years.
Up to date, however, the development of the
biomass energy technologies is still unbalanced and
far from blooming [68]. Few of them, such as
march gas technology, has been found commer-
cial applications; the others, for instance biomass
power, biomass briquettes combustion, bioethanol
and biodiesel, are still difficult to reach the commer-
cial requirement and need more state support; more
researches are still in the lab scale. Enze Min is the
founder in the field of biomass conversion in China
 REVIEW
[69]. A ‘Min Enze Energy Chemical Industry Award’
has been jointly set by the Chinese Academy of En-
gineering (CAE) and Sinopec groups to promote
the progresses of biomass energy technology and en-
courage the outstanding contributors in this field.
In the biomass fuel field, Du et al. successfully
developed a new biodiesel technology, named as
SRCA biomass green technology [68], which was
based on the near-critical/supercritical methanol-
ysis reaction. Most kind of the oil such as swill-
cooked oil, acidic oil, animal fat, vegetable oil can
be used as feedstock. Reducing the reaction tem-
perature and pressure increases the conversion of
the feedstock but promotes the separation of the
products. This process has been applied in the na-
tional biodiesel demonstration project (60 kt/a) and
gone into operation in 2009. In addition, Sinopec
has developed a new technology, which converts
the waste cooking oil and seaweed to aviation fuel.
In April of 2013, the home-developed biomass avi-
ation fuel 1# completed its maiden flight success-
fully [70]. Compared with traditional aviation fuel,
biomass aviation fuel reduces the CO2 emission by
55–92%. What is more, the modification of the en-
gine is not necessary. Moreover, some researchers
propose the second-generation biodiesel synthesis
route, which is based on the catalytic hydrogena-
tion. Generally speaking, it is feasible to transform
animal fat and vegetable oil to unbranched alka-
nes by hydrodeoxygenation and isomerization re-
actions [71]. A biodiesel process based on the hy-
drodeoxygenation of vegetable oil has been devel-
oped and industrialized by Sakatehewan Science Re-
search Council in Canada [72]. In China, a team
from Tsinghua University put forward the process
which integrates the hydrofining and hydrocrack-
ing process for preparing biodiesel from bio oil and
petroleum distillates [73]. Yao et al. designed a su-
percritical solvent for the fatty acid methyl ester hy-
drogenation reaction. The reaction pressure and the
feed ratio of H2 and fatty acid methyl ester were
greatly reduced keeping the conversion and selectiv-
ity as high as 99% [74].
The exploitation of cellulose plays a very impor-
tant part in the biomass development. A lot of chem-
icals, such as synthesis gas, pyrolysis oil, glucose,
ethanol and aromatics, can be produced from cellu-
lose. Increasing the selectivity of the products com-
ing from cellulose is a challenge work because of
the complex chemical bonds in the cellulose (C–
O, C–C, C–H, O–H, etc.). Some progresses have
been achieved in the other countries. For instance,
Anellotech company developed a biomass pyroly-
sis technology to produce aromatic; Virent com-
pany realized producing xylene by the aqueous re-
forming reaction. In China, Zhang et al. designed
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Xie et al. 175
a Ni-W2 C/AC difunctional catalyst for the trans-
formation of cellulose to EG with the yield up to
50–74% [75,76]. Liu’s group reported the conver-
sion of cellulose to polyhydric alcohols via green
and energy efficient approaches [77,78], develop-
ing a new route to produce propylene glycol, lac-
tic acid, in which the WO3 -Ru/C catalyst selectively
broke the C–C bond and increased the selectivity of
the product [79]. Wang et al. reported that Pb(II)
can effectively catalyze the transformation of cellu-
lose to lactic acid, the yield reached to above 60%
when the microcrystalline cellulose was used as feed-
stock [80]. The unpurified cellulose, such as sugar-
cane and grass, can be directly fed in this catalytic
system.
As an ideal and clean energy carrier, interest in
hydrogen is rising due to alleviating the dependence
on fossil fuels and reducing pollution and green-
house gas emissions [81]. However, current utilizing
of hydrogen energy is still hindered by several key
issues, in particular current unsustainable produc-
tion and storage process with high greenhouse gas
emissions, low-energy efficiency and atom economy.
Therefore, improving the sustainability of product
and efficiency of storage is crucial for building hy-
drogen infrastructure if considering the increasing
demand in energy sector. Xie and co-workers re-
cently proposed a concept of ‘green hydrogen
science’ [5], which can be intended to design and
construct the hydrogen energy system with a high
degree of atom economy and sustainability. By
putting forward a theoretical view of ‘design and
construction of a hydrogen energy system covering
low-carbon production and highly efficient storage
based on the concept of green hydrogen science’, a
technology roadmap of ‘low-carbon hydrogen pro-
duction and highly efficient storage’ was used to
identify the strategic goals, barriers and key activ-
ities, attempting to solve many related challenging
scientific issues (Fig. 7). For the purpose of a sus-
tainable and green production process, catalysis sci-
ence also plays an extremely important role. During
the hydrogen production, highly value-added chem-
ical coproducts such as coal and aromatic can be ob-
tained via increasing the degree of unsaturation of
carbon containing products from the cleaving of the
first C–H bond by methane decomposition and non-
oxidative dehydroaromatization. These production
processes show high atom economy and relative
greenness, according to the demand of ‘low-carbon
production’. In the course of non-oxidative reaction,
the carbon containing products with a high degree
of unsaturation is notoriously difficult to control.
A sharp reduction of production efficiency is usu-
ally observed because of a rapid deactivation of cat-
alyst caused by coke accumulation. In this respect,
 176 Natl Sci Rev, 2015, Vol. 2, No. 2
ria
st
du
s
In
source
Electrolysis of water Photocatalysis
e mo
With thermochemical cycle yd
log
tio of re
Based on renewable hno
ec
energy
Bioanalysis T 2030
rbon ra
Hydrocarbon reforming
in
Low carbon conversion
ughs
ak thro
en/ca
Reforming +CCS
technologies
Bre
hydrog
Biomass alternative
Coal gasification
route
Coal gasification +
CCS technologies
The
Green degree
Figure 7. Roadmap of low-carbon hydrogen production technologies. Adapted from
[5] C 2014 Science China Press.
many intense research efforts on fabricating a high-
performance catalyst have been devoted to inhibit
a fast deactivation caused by the build-up of carbon
deposits [82]. Besides, a promising long-term strat-
egy of hydrogen production is photocatalytic wa-
ter splitting by utilizing solar energy. Through un-
derstanding the photoexcited charge separation and
recombination behavior and the mechanism of hy-
drogen production, the preparation of a high effec-
tive visible-light-driven photocatalyst is the key to a
breakthrough for the improvement of the solar en-
ergy conversion efficiency [83,84].
Carbon emission reduction policy is one of the
core contents of green chemical engineering, in
which the CO2 emission reduction, trapping, stor-
age and chemical utilization are key measures. CO2
is one of the ‘chemical blocks’ and can be used for
the production of hydrocarbon, methanol, formic
acid, aldehyde, ether, ester, acrylic acid, salicylic acid,
organic carbonates and a series of organic chemi-
cals and high-value-added fine products. Currently,
the processes of transformation of CO2 to urea, am-
monium carbonate, carbonate, CO, carbonic ester
are partly or fully industrialized. On the other hand,
some approaches, such as CO2 hydrogenation to
methanol, reforming of CO2 and methane to synthe-
sis gas, are not mature yet. Mitsui Chemicals Inc. has
set up the first demonstration plant in the world (100
t/a) for the hydrogenation of CO2 to methanol. But
in China, this process is still in the stage of laboratory
research. The technologies of reforming of CO2 and
methane to synthesis gas is mostly in the laboratory
scale or just a few pilot tests were ever reported such
as the SPARG process by Haldor Topsoe [85] and
the CALCOR process in Germany [86]. In China, it
was reported that a mesoporous zirconia supported
metal catalyst with excellent catalytic activity and
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stability developed by China Petroleum University
n
io
ot (Hua Dong) [87]. In addition, it is also reported by
m
ro
lp Sinopec SRIPT [88] and Shanghai Advanced Re-
2040
search Institute [89] respectively that novel non-
on
ati
str
n noble metal catalysts can be employed as effective
catalysts in CH4 /CO2 reforming, with lifetime of
catalysts exceeding 1000 h.
ies
olog The photocatalytic conversion of CO2 is one of
techn
key
the ideal ways for removing CO2 fundamentally on
a long view. In nature, plants convert CO2 and wa-
2020
ter into glucose by using solar energy. Therefore,
the scientists are making great efforts to convert
CO2 to CO, methane, methanol, formic acid and
formaldehyde as fuel or chemicals by photocatalysis
processes. The main challenge of these processes is
the limitation of photocatalytic efficiency. Li’s group
have researched a lot about the photoelectric, pho-
tothermal and photocatalytic conversion of CO2
and gained plentiful achievements. They found that
a suitable promoter catalyst greatly reduces the over-
potential of the reduction reaction, and improves the
photocatalytic efficiency [90]. This result prompts a
new research climax in this field.
DISCUSSION ON SOME SCIENTIFIC
PROBLEMS FROM INDUSTRIAL POINT
OF VIEW
From the industrial point of view, high efficiency
and green low carbon will be more emphasized
in the future energy chemical catalysis. Therefore,
more attentions should be paid to the basic sci-
entific problems including catalysis efficiency, ho-
mogenous catalysis in heterogonous system and cat-
alyst design directed by in situ characterization.
Catalytic efficiency related with diffusion
The improvement method of catalysis property was
usually focused on the adjustment of active sites,
such as their types, amounts, activity and stability.
However, out of active sites, diffusion is another crit-
ical factor impacting catalyst performance and the ef-
ficiency of active sites. As mentioned above, zeolites
were employed as catalysts in lots of chemical pro-
cesses, like heavy oil refining, MTO/MTP, toluene
disproportionation and alkylation of aromatics, etc.
The accessibility of reactant molecules to active sites
was usually restricted by the diffusion limit, leading
to low efficiency in catalysis. Therefore, improving
diffusion to promote the catalysis efficiency by mod-
ulating pore structure and morphology will be a con-
siderable scientific problem.
To improve catalysis efficiency, the trends for ze-
olitic catalysts should be noticed as follows: the first
 REVIEW
(A) a b
1
Φ = 0.1
1.0
Full use
C/Cs 0.5 η/-
Φ = 0.2
Φ = 10 Unutilised
0.0
volume
0.1 Poor use
1 0 1 0.1 1 10
x/L Φ/-
c
Concentration profile Thiele modulus Effectiveness factor
cosh(Φx/L ) rintrinsic kv r tanh Φ
C = Cs Φ= Φ = observed =
cosh(Φ ) rdiffusion = L r intrinsic
Deff
Figure 8. (A) The scheme (adapted from [104] C 2008 The Royal Society of Chemistry) and (B) the real determinations of catalytic effectiveness with
Thiele Modulus for conventional zeolite (filled triangles) and hierarchical zeolite (filled asterisks). Adapted from [100] C 2014 The Royal Society of
Chemistry.
is synthesis and application of zeolite materials with
larger pores, such as large or super microporous zeo-
lite, mesoporous and macroporous materials, which
were synthesized to meet the demand in catalysis
conversion of heavy oil, heavy aromatics and bio-
logical macromolecules. Lots of new type zeolites
with large or superlarge micropores, including VPI-
5, UTP-1, ECR-34, ITQ-21, ITQ-33, SSZ-35, SSZ-
44 etc. [91] and mesoporous materials, M41-S and
SBA-15 [92] etc. were found or synthesized in re-
cent years. At present, however, low hydrothermal
stability for the inherent amorphous pore wall hin-
dered the industrial applications of mesoporous ma-
terials. Secondly, the miniaturization of zeolites by
constructing nanocrystals and nanofilms [93] was
usually considered as another method to improve
utilization efficiency of active sites, in which diffu-
sion length in micropores was shortened by reducing
crystal size. However, there are still some unavoid-
able challenges in the application of nanomaterials,
such as high synthesizing cost, low stability for easy
aggregation. Moreover, the catalyst/product separa-
tion problem emerged in the heterogeneous reac-
tion, leading to the recycle problem of catalyst in in-
dustry, especially in the solid/liquid phase system in-
volving nanozeolites. The third measure which may
be taken to improve diffusion in zeolite catalyst is
constructing multiple pore structure to develop hi-
erarchical porous materials [94]. Based on such con-
cept, Xie’s group have developed lots of synthe-
sis methods and industrial applications of hierarchi-
cal zeolites [95]. Hierarchical ZSM-5, Silicalite-1,
Beta and SAPO-34 zeolites have been successively
developed by templating method, steam-assisted-
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Xie et al. 177
(B) 1.0
0.8
Effectiveness factor (a.u.)
0.6
0.4
0.2
0.0
0.1 1 10
Thiele modulus (a.u.)
Φ
crystallization, post-alkaline treatment, etc. More-
over, outstanding performances have been found
in the catalyzing supercritical toluene dispropor-
tionation [96], conversion of heavy aromatics [97],
alkylation of benzene with ethylene [98], transalky-
lation of multi-isopropyl benzene [99], methanol
conversion to olefin/propylene [41] etc., some of
which have found applications in industry. More-
over, a determination strategy for diffusivity was de-
veloped via thiele modulus analysis which provid-
ing direct experimental evidence for the remarkable
improvement of utilization efficiency in hierarchi-
cal MFI zeolites catalyst [100] (Fig. 8). Construc-
tion of hierarchical porous structure is considered
an important method to promote diffusion and uti-
lization efficiency of zeolite catalysts which indicated
a meaningful direction for catalysis research. Many
other groups such as Shi’s group [101], Tang’s group
[102] and Xiao’s group [103], etc. in China have
also done many innovative works on the hierarchi-
cal porous zeolite materials in recent years.
Homogeneous catalysis within
heterogeneous catalysts
It is known that the efficiency of homogeneous cat-
alyst is much higher than heterogeneous catalyst in
liquid phase. However, unsustainable homogeneous
catalysts often suffered from separation problem and
led to environmental hazard. Therefore, developing
high efficient heterogeneous catalyst with homoge-
neous catalysis property is still challenging in green
chemistry.
 178 Natl Sci Rev, 2015, Vol. 2, No. 2
Homogeneous catalysis in heterogeneous sys-
tem, especially the development of nanoreactor
based on the characteristic of enzyme structure, has
drawn lots of attentions in recent years. Mn (Salen)
molecular catalyst which demonstrated high activ-
ity in selective oxidation reaction was constructed in
the micropores of zeolite by Jacobsen et al. [105].
Subsequently, chiral molecular catalyst assembled in
nanopores of mesoporous materials was found pos-
sessing higher chiral selectivity and subsequently,
the concept of space confinement effect was also
proposed [106]. Lots of innovative progresses about
nanoreactor have been reported by Yang and Li’s
group. They designed a heterogeneous asymmet-
ric catalyst by confining nanoparticles within nan-
otubes and found the promotion of reactant con-
centration and accelerative effect of dual-centered
activated coupling in confined space of nanoreator
[107]. Such dual-centered activated coupling effect
can even be observed in the low catalyst content
which demonstrated even higher performance than
homogeneous catalysts. A non-acid molecular cat-
alyst was then developed and employed for hydra-
tion of epoxide in which the yield of MEG can result
up to 96% even at the condition of H2 O/EO mo-
lar ratio as low as 2 under mild reaction conditions
[108]. Because of synergic coupling effect, the sig-
nificant promotion of MEG, from 10 to 74 wt%, re-
markably reduced energy cost in distils procedure.
Therefore, the cooperation activation effect of the
molecular catalysts in the nanoreactors resulted in
enormous enhancement of catalytic activity, offering
a new strategy of homogeneous catalysis in hetero-
geneous system and will prompt potential applica-
tions in green catalysis.
Reaction controlled phase transfer catalyst is also
a heterogeneous catalysis system with homogeneous
characteristics [33,109], such as heteropolyphos-
phatotungstate catalysts Q3 [PW4 O16 ] (Q repre-
sents quaternary ammonium cationic). Such cat-
alysts are usually insoluble in reactant system at
first, but become soluble under the presence of
H2 O2 . Therefore, in fact, the propylene epoxidation
reaction is a homogeneous catalysis process with
this kind of catalyst. Along with the consumption
of H2 O2 after reaction, catalyst becomes insoluble
again and gradually precipitates from the reaction
system, and can be conveniently recycled. Such spe-
cial catalyst/procedure has been employed in pro-
cess of producing epoxy chlorohexane [34,110] and
is now being developed for application in other
green processes, such as the production of propylene
epoxide and epoxy chloropropane, etc.
The combination of nanocatalysis with mem-
brane separation is a green feasible technique by
which the efficiency of heterogeneous catalysis may
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be significantly promoted. Membranes separation
techniques have experienced rapid expansion re-
cently [111]. Recently, a new kind of slurry reaction
procedure was successfully developed by employing
nanosized hollow Ti-Silicalite zeolite (HTS) as ox-
idation catalyst [27] and combining membrane
separation technique [112–114]. On the basis of
keeping high catalysis performance, separation and
recycle problem was overcome by such method.
Development of in situ or operando
techniques for characterization of
heterogeneous catalysts or mechanism
Considered as important techniques for cataly-
sis, advanced operando or in situ characterization
studies demonstrated direct evidences in observing
and researching structure, active sites and reaction
mechanism information, providing theoretical guid-
ance for design and optimization of catalyst. Early
in the 1950s, in situ IR spectra have been employed
in the study of NH3 absorbance on Pd/SiO2 -Al2 O3
catalyst by Eischens [115]. With the development
of in situ or operando characterization technique,
the studies of active sites have been deep into the
atomic level and intermediate state in catalysis now.
It is found that just tiny structure conversion of cat-
alyst often significantly impacted reaction perfor-
mance which was uncovered by in situ characteriza-
tion studies [116]. The status of active sites in catal-
ysis can be only characterized by in situ techniques
by which the fundamental insight made the ratio-
nal design of catalysts possible. Besides, some ad-
vanced in situ imaging techniques such as transmis-
sion X-ray microscope, combined μ-XRD-CT and
μ-absorption-CT (CT = computed tomography)
technique by focusing hard X-ray were developed
and applied in syngas conversion which realized the
3D tracing of composition and structure in Fe-based
catalyst by Weckhuysen et al. [117]. They also stud-
ied the revolution of pore structure, composition,
coking in the gradual inactivation process of refin-
ing catalyst by in situ imaging technique [118]. The
development of powerful spectra characterization
technique in micro-nanometer scale makes it possi-
ble to reveal the relevance between macroscopic and
submicroscopic domains.
Big progresses have been made also in China
in the field of in situ characterization technique.
Li et al. [119,120] studied the synthesis and re-
action theory of Fe-, V- and Mo- catalyst by in
situ ultraviolet Raman spectra and realized the in
situ detecting of zeolite under hydrothermal condi-
tion using self-developed Raman spectrometer. Lots
of related reports, including the design, synthesis,
 REVIEW
identification of active species and catalysis mech-
anism of heteroatomic zeolite can also be found in
recent years [121,122]. By in situ synchrotron ra-
diation technique, Bao et al. studied the confined
space catalysis in carbon nanotubes [123,124] and
interface-confined ferrous centers on nano Pt par-
ticles [125]. And by operando IR or Raman spec-
tra, Wan et al. studied the catalysts for C1 –C3 alkane
conversion [126,127].
As the representative of the advanced research
level in catalysis field, more attentions should be
paid to develop in situ and operando characterization
techniques at present and in future.
CONCLUSION AND OUTLOOK
The scientific connotation for sustainable develop-
ment of energy chemical engineering is involved
in green carbon science, which means optimization
of carbon atom economics based on high efficient
catalysis and carbon emission reduction. Centered
on the concept of green and low carbon, lots of in-
novations on catalytic techniques have been pro-
gressed on higher efficient or green processes as well
as alternative non-oil routes in China, which include
high efficient conversion of oil, clean utilization of
coal and natural gas, development of sustainable re-
sources and clean energy, etc. From the view of
industry, fundamental researches on scientific prob-
lems such as diffusion and efficiency of catalysts, ho-
mogeneous catalysis in heterogeneous system, in situ
characterization in industrial catalysis, etc., are defi-
nitely helpful to develop new catalytic techniques for
sustainable energy chemical industry.
It is believed that environmental friendly and
low-carbon catalysis will play an important role lead-
ing to sustainable development of energy chemical
industry in China.
FUNDING
This work was supported by the National Natural Science Foun-
dation of China (91434102).
REFERENCES
1. Anastas, PT and Warner, J. Green Chemistry Theory and Prac-
tice. Oxford: Oxford University Press, 1998.
2. Anastas, PT and Kirchhoff, MM. Origins, current status, and fu-
ture challenges of green chemistry. Acc Chem Res 2002; 35:
686–94.
3. He, MY and Sun, YH. Green carbon science: scientific basis for
the efficient utilization of fossil energy with low emission. Sci
China Chem 2011; 41: 925–32.
4. He, MY, Sun, YH and Han, BX. Green carbon science: scien-
tific basis for integrating carbon resource processing, utiliza-
tion, and recycling. Angew Chem Int Ed 2013; 52: 9620–33.
Downloaded from https://academic.oup.com/nsr/article-abstract/2/2/167/2097218
by guest
on 21 February 2018
Xie et al. 179
5. Xie, ZK, Jin, ZH and Wang, YD. Design and construction of a
hydrogen energy system covering low-carbon production and
highly efficient storage based on the concept of green hydrogen
science. Sci China Chem 2014; 44: 6–12.
6. Simanzhenkov, V, Oballa, MC and Kim, G et al. Technology
for producing petrochemical feedstock from heavy aromatic oil
fractions. Ind Eng Chem Res 2010; 49: 953–63.
7. Zhou, JH, Min, EZ and Shu, XT et al. A zeolite Y material
with dual porosity and its preparation method. China Patent:
CN200810227657.6, 2008.
8. Zhao, L, Shen, BJ and Gao, JS et al. Investigation on the mech-
anism of diffusion in mesopore structured ZSM-5 and improved
heavy oil conversion. J Catal 2008; 258: 228–34.
9. Tan, QF, Bao, XJ and Song, TC et al. Synthesis, characteriza-
tion, and catalytic properties of hydrothermally stable macro–
meso–micro-porous composite materials synthesized via in situ
assembly of preformed zeolite Y nanoclusters on kaolin. J Catal
2007; 251: 69–79.
10. Tatsumi, T and Nishimura, Y (ed.). Development Technology of
Zeolite Catalyst. Japan: CMC Publishing Co., Ltd, 2010, 39.
11. Liu, YD, Gao, L and Zong, BN et al. Recent advances in heavy
oil hydroprocessing technologies. Recent Pat Chem Eng 2009;
2: 22–36.
12. Liu, YD, Gao, L and Zong, BN et al. Development of slurry bed
technologies for upgrading heavy oils. Chem Ind Eng Prog 2010;
29: 1589–96.
13. Gao, L, Liu, YD and Wen, LY et al. The effect of supercritical
water on the hydroconversion of Tahe residue. AIChE J 2010;
56: 3236–42.
14. Zhu, YX and Xu, H. Improvemant and development of S-Zorb
process. Pet Refin Eng 2009; 39: 7–12.
15. Long, J, Lin, W and Dai, Z. From detailed desulfurization mech-
anism to successful commercial application I. Features and ad-
cantages of S Zorb technology. Acta Pet Sin (Petro Proc Sect)
2015; 31: 1–6.
16. Liu, L. Comparison of FCC naphtha desulfurization process
schemes and application analysis. Pet Refin Eng 2008; 38: 11–
5.
17. Yang, YX, Zhang, YL and Li, C et al. Ultra deep adsorptive desul-
furization of solvent oils by Ni/ZnO adsorbent. Petrochem Tech
2008; 37: 243–6.
18. Corma, A, Martinez, C and Sauvanaud, L. New materials as FCC
active matrix components for maximizing diesel (light cycle oil,
LCO) and minimizing its aromatic content. Catal Today 2007;
127: 3–16.
19. Guo, R, Shen, BX and Fang, XC et al. Study on performances of
diesel deep hydrodesulfurization catalyst. Pet Refin Eng 2011;
41: 31–4.
20. Jing, DH, Guo, R and Yao, B et al. Study on production of clean
diesel oil of Euro-specifications in high space velocity condi-
tions. Pet Refin Eng 2011; 41: 1–3.
21. Yang, P, Xin, J and Nie, H et al. Research advances in the hy-
droconversion of tetralin. Pet Proc Petrochem 2011; 42: 1–6.
22. Zheng, JL, Qian, B and Qi, XL et al. Research on direct produc-
tion of BTX aromatic from light cycle oil. Petrochem Tech 2014;
43: 124–5.
 180 Natl Sci Rev, 2015, Vol. 2, No. 2
23. Chauvin, Y, Hirschauer, A and Olivier, H. Alkylation of isobutane with 2-butene
using 1-butyl-3-methylimidazolium chloride-aluminium chloride molten salts
as catalysts. J Mol Catal 1994; 92: 155–65.
24. Huang, CP, Liu, ZC and Xu, CM et al. Effects of additives on the properties of
chloroaluminate ionic liquids catalyst for alkylation of isobutane and butene.
Appl Catal A 2004; 277: 41–3.
25. Liu, Y, Hu, RS and Xu, CM et al. Alkylation of isobutene with 2-butene using
composite ionic liquid catalysts. Appl Catal A 2008; 346: 189–93.
26. Cui, J, With, JD and Klusener, PAA et al. Identification of acidic species in
chloroaluminate ionic liquid catalysts. J Catal 2014; 320: 26–32.
27. Su, B, Chen, SB and Meng, XK et al. Green production technology of caprolac-
tam. Sci China Chem 2014; 44: 40–5.
28. Lin, M, Shu, XT and Wang, XQ et al. Titanium-silicalite molecular sieve and
the method for its preparation. US Patent: 6475465, Nov 05, 2002.
29. Zhu, B. Study on catalytic material used in HPPO process. Acta Pet Sin (Petro
Proc Sect) 2013; 29: 223–7.
30. Shi, CF, Lin, M and Long, J et al. Deactivation and regeneration of titanosilicate
catalyst used in HPPO pilot test. Acta Pet Sin (Petro Proc Sect) 2013; 29: 864–9.
31. Li, XF, Gao, HX and Jin, GJ et al. Influence of silylation on catalytic performance
of Ti/HMS molecular sieve. Chin J Catal 2007; 28: 551–6.
32. Jin, GJ, Gao, HX and Yang, HY et al. Study on characterization and catalytic
performance for propylene epoxidation of Ti/HMS catalyst prepared by graft-
ing technology. J Mol Catal 2010; 24: 6–12.
33. Xi, ZW, Zhou, N and Sun, Y et al. Reaction-controlled phase-transfer catalysis
for propylene epoxidation to propylene oxide. Science 2001; 292: 1139–41.
34. Gao, S and Xi, ZW. Reaction-Controlled Phase-Transfer Catalysts for Epoxida-
tion of Olefins. In: Oyama, ST (ed.). Mechanisms in Homogeneous and Hetero-
geneous Epoxidation Catalysis. Amsterdam: Elsevier, 2007, 429.
35. Yu, FP, Cai, H and He, WJ et al. Synthesis and characterization of a poly-
mer/multiwalled carbon nanotube composite and its application in the hydra-
tion of ethylene oxide. J Appl Polym Sci 2010; 115: 2946–54.
36. Li, YN, Yu, FP and He, WJ et al. The preparation and catalytic performance of
graphene-reinforced ion-exchange resins. RSC Adv 2015; 5: 2550–61.
37. Liu, ZM, Wei, YX and Li, JZ et al. Chapter 1: Important progresses on industrial
application of zeolitic catalysts and DMTO technologies. In: Yu, JH and Yan,
WF (eds.). Chemistry of Nanoporous Materials: Catalysis and Function. Beijing:
Science Press, 2013, 21–30.
38. Li, JZ, Wei, YX and Liu, ZM et al. Observation of heptamethylbenzenium cation
over SAPO-type molecular sieve DNL-6 under real MTO conversion conditions.
J Am Chem Soc 2012; 134: 836–9.
39. Liu, HX, Xie, ZK and Zhang, CF et al. Study on synthesis of SAPO-34 molecular
sieve using composite template TEAOH-morpholine. Chin J Catal 2004; 25:
702–10.
40. Xie, ZK, Liu, ZC and Wang, CM et al. Catalytic conversion of methanol to
olefins: some progresses on catalytic materials and reaction mechanism [oral
presentation]. Presented at the 15th International Congress on Catalysis,
Munich, Germany, 2012.
41. Yang, HQ, Liu, ZC and Xie, ZK et al. Synthesis and catalytic performances of
hierarchical SAPO-34 monolith. J Mater Chem 2010; 20: 3227–31.
42. Wang, CM, Wang, YD and Xie, ZK et al. Methanol to olefin conversion on
HSAPO-34 zeolite from periodic density functional theory calculations: a com-
plete cycle of side chain hydrocarbon pool mechanism. J Phys Chem C 2009;
113: 4584–91.
43. Wang, CM, Wang, YD and Xie, ZK et al. Catalytic activity and selectivity of
methylbenzenes in HSAPO-34 catalyst for the methanol-to-olefins conversion
from first principles. J Catal 2010; 271: 386–91.
Downloaded from https://academic.oup.com/nsr/article-abstract/2/2/167/2097218
by guest
on 21 February 2018
REVIEW
44. Wang, CM, Wang, YD and Xie, ZK et al. Insights into the reaction mechanism
of methanol-to-olefins conversion in HSAPO-34 from first principles: are olefins
themselves the dominating hydrocarbon pool species? J Catal 2013; 301: 8–
19.
45. Teng, JW and Xie, ZK. Novel binder-less hierarchical ZSM-5 catalysts for
olefins catalytic cracking to produce propylene. Sci China Chem 2015,
doi:10.1360/N032014-00296.
46. Tian, T, Qian, WZ and Sun, YJ et al. Aromatization of methanol on Ag/ZSM-5
catalyst. Mod Chem Ind 2009; 29: 55–9.
47. Jian, WF, Wei, F and Wei, T et al. An apparatus and process for continu-
ous aromatization and catalyst regeneration. China Patent: CN 200810102684,
2008.
48. Zou, W, Kong, DJ and Zhu, ZH et al. A process for PX production by benzene
alkylation with methanol. China Patent: CN 200510028770, 2005.
49. Kong, DJ, Liu, ZC and Fang, DY. Epitaxial growth of core-shell ZSM-5/Silicalite-
1 with shape selectivity. Chin J Catal 2009; 30: 885–90.
50. Zou, W, Yang, DQ and Xie, ZK et al. Selective methylation of toluene with
methanol over HZSM-5 zeolite modified by chemical liquid deposition. Chem
React Eng Tech 2006; 22: 305–9.
51. Zou, W and Kong, DJ. A process for PX production by toluene alkylation with
methanol. China Patent: CN 200910057232.X, 2009.
52. Xu, L, Liu, ZM and Zhang, ZX et al. An online modification method of catalyst
for toluene methylation. China Patent: CN 200610011662.4, 2006.
53. Zhao, S, Liu, XW and Huo, CF et al. Surface morphology of Hägg iron carbide
(χ -Fe5 C2 ) from ab initio atomistic thermodynamics. J Catal 2012; 294: 47–53.
54. Huo, CF, Wu, BS and Gao, P et al. The mechanism of potassium promoter:
enhancing the stability of active surfaces. Angew Chem Int Ed 2011; 50: 7403–
6.
55. Huo, CF, Li, YW and Wang, J et al. Insight into CH4 formation in iron-catalyzed
Fischer-Tropsch synthesis. J Am Chem Soc 2009; 131: 14713–21.
56. Deng, LJ, Huo, CF and Li, YW et al. Density functional theory study on surface
CxHy formation from CO activation on Fe3 C(100). J Phys Chem C 2010; 114:
21585–92.
57. Li, YW, Xu, J and Yang, Y. Diesel From Syngas. New York: Wiley, 2009.
58. Li, YW and De, KA. Industrial Case Studies. New York: Wiley, 2013.
59. Liu, ZY, Shi, SD and Li, YW. Coal liquefaction technologies-development in
China and challenges in chemical reaction engineering. Chem Eng Sci 2010;
65: 12–7.
60. Kang, J, Cheng, K and Wang, Y et al. Mesoporous zeolite-supported ruthenium
nanoparticles ashighly selective Fischer-Tropsch catalysts for the production of
C5-C11 isoparaffins. Angew Chem Int Ed 2011; 50: 5200–3.
61. Kang, J, Zhang, S and Wang, Y et al. Ruthenium nanoparticles supported on
carbon nanotubes as efficient catalysts for selective conversion of syngas to
diesel fuel. Angew Chem Int Ed 2009; 48: 2565–8.
62. Huang, YY, Guo, YL and Wang, YB. Ethylene glycol electrooxidation on core-
shell PdCuBi nanoparticles fabricated via substitution and self-adsorption pro-
cesses. J Power Sources 2014; 249: 9–12.
63. Lin, L, Pan, PB and Zhou, ZF et al. Cu/SiO2 catalysts prepared by the sol-gel
method for hydrogenation of dimethyl oxalate to ethylene glycol. Chin J Catal
2011; 32: 957–69.
64. Li, T. Review on current development of syngas to glycol technologies in China.
Fine Chem Ind Raw Mater Intermed 2012; 12: 40–3.
65. Jiang, ZH. The composition of syngas to ethylene glycol technical progress
abroad and at home. Synth Tech Appl 2010; 25: 27–30.
66. Zhou, JF, Liu, XQ and Liu, DH. Progress and perspective of synthesis of ethylene
glycol from syngas via oxalate. Chem Ind Eng Prog 2009; 28: 47–50.
 REVIEW
67. Guo, XG, Fang, GZ and Bao, XH et al. Direct, nonoxidative conversion of
methane to ethylene, aromatics, and hydrogen. Science 2014; 344: 616–9.
68. Wu, CZ, Zhou, ZQ and Yin, XL et al. Current status of biomass energy develop-
ment in China. Trans Chin Soc Agri Mach 2009; 40: 91–9.
69. Min, EZ and Zhang, LX. Analysis Report of Biomass Refining & Chemical In-
dustry. Beijing: Science Press, 2013.
70. China’s no. 1 biological fuel test success. Energy Conserv Emiss Reduct Pet
Petrochem Ind 2013; 3: 19.
71. Stumborg, M, Wong, A and Hogan, E. Hydroprocessed vegetable oils for diesel
fuel improvement. Bioresour Technol 1996; 56: 13–8.
72. Zhou, JX. Development and future of full green chemical industry. Chem Eng
Des 2010; 20: 3–7.
73. Yuan, RB, Wang, YJ and Piao, XL et al. A process for biodiesel prduction by
integrated hydrogenation. China Patent: CN 200710065393.4, 2007.
74. Yao, ZL. Research on synthesis of fatty alcohols from fatty acid methyl ester by
supercritical hydrogenation technology. Doctoral dissertation. Beijing Sinopec
Research Institute of Petroleum Processing, 2008.
75. Ji, N, Zhang, T and Zheng, MY et al. Direct catalytic conversion of cellulose
into ethylene glycol using nickel-promoted tungsten carbide catalysts. Angew
Chem Int Ed 2008; 47: 8510–3.
76. Wang, AQ and Zhang, T. One-pot conversion of cellulose to ethylene glycol
with multifunctional tungsten-based catalysts. Acc Chem Res 2013; 46: 1377–
86.
77. Luo, C, Wang, S and Liu, HC. Cellulose conversion to polyols catalyzed by
reversibly-formed acids and supported ruthenium clusters in hot water. Angew
Chem Int Ed 2007; 46: 7636–9.
78. Yan, N, Zhao, C and Luo, C et al. One step conversion of cellobiose to C6 -
alcohols using a ruthenium nanocluster catalyst. J Am Chem Soc 2006; 128:
8714–5.
79. Liu, Y, Luo, C and Liu, HC. Tungsten trioxide promoted selective conversion of
cellulose into propylene glycol and ethylene glycol on a ruthenium catalyst.
Angew Chem Int Ed 2012; 51: 3249–53.
80. Wang, Y, Wang, B and Deng, W et al. Chemical synthesis of lactic acid from
cellulose catalysed by lead(II) ions in water. Nat Commun 2013; 4: 2141.
81. Navarro, RM, Pena, MA and Fierro, JLG. Hydrogen production reactions from
carbon feedstocks: fossil fuels and biomass. Chem Rev 2007; 107: 3952–
91.
82. Jin, ZH, Liu, S and Xie, ZK et al. Methane dehydroaromatization by Mo-
supported MFI-type zeolite with core-shell structure. Appl Catal A-Gen 2013;
453: 295–301.
83. Wen, FY, Yang, JH and Zong, X et al. Photocatalytic hydrogen production uti-
lizing solar energy. Prog Chem 2009; 21: 2285–302.
84. Maeda, K and Domen, K. Photocatalytic water splitting: recent progress and
future challenges. J Phys Chem Lett 2010; 1: 2655–61.
85. Udengaard, NR, Hansen, JHB and Hanson, DC et al. Sulfur passivated reform-
ing process lowers syngas H2 /CO ratio. Oil Gas J 1992; 90: 62–7.
86. Teuner, SC, Neumann, P and Linde, FV. CO through CO2 reforming-the cal-
cor standard and calcor economy processes. Oil Gas Eur Mag 2001; 27:
44–6.
87. Rezaei, M, Alavi, SM and Yan, ZF et al. Effects of K2 O promoter on the activ-
ity and stability of nickel catalysts supported on mesoporous nanocrystalline
zirconia in CH4 reforming with CO2 . Energy Fuel 2008; 22: 2195–202.
88. Liu, ZC, Zhou, J and Cao, K et al. Highly dispersed nickel loaded on meso-
porous silica: one-spot synthesis strategy and high performance as catalysts
for methane reforming with carbon dioxide. Appl Catal B-Environ 2012; 125:
324–30.
Downloaded from https://academic.oup.com/nsr/article-abstract/2/2/167/2097218
by guest
on 21 February 2018
Xie et al. 181
89. Sun, NN, Wen, X and Wang, F et al. Catalytic performance and characterization
of Ni-CaO-ZrO2 catalysts for dry reforming of methane. Appl Surf Sci 2011; 257:
9169–76.
90. Yang, JH, Wang, DG and Li, C et al. Roles of cocatalysts in photocatalysis and
photoelectrocatalysis. Acc Chem Res 2013; 46: 1900–9.
91. Wan, Y and Zhao, DY. On the controllable soft-templating approach to meso-
porous silicates. Chem Rev 2007; 107: 2821–60.
92. Liu, ZC, Wang, YD and Xie, ZK. Some thoughts on future development of ze-
olitic catalysts from industrial catalysis point of view. Chin J Catal 2012; 33:
22–38.
93. Zhang, H, Ma, Y and Song, K et al. Nano-crystallite oriented self-assembled
ZSM-5 zeolite and its LDPE cracking properties: effects of accessibility and
strength of acid sites. J Catal 2013; 302: 115–25.
94. Su, BL, Sanchez, C and Yang, XY. Hierarchically Structured Porous Materials:
From Nanoscience to Catalysis, Separation, Optics, Energy, and Life Science.
Weinheim: Wiley-VCH, 2011.
95. Xie, ZK, Liu, ZC and Wang, YD. Hierarchical construction of porous materials
and their catalysis. In: Yu, JH and Yan, WF (ed.). Chemistry of Nanoporous
Materials: Catalysis and Function. Beijing: Science Press, 2013, 69–123.
96. Liu, ZC, Wang, YD and Xie, ZK et al. Frontiers of modern chemical engineer-
ing, metallurgy, and material technologies. In: Wang, JK (ed.). Proceedings of
the 7th Chinese Academy of Engineering Symposium. Beijing: Chem Ind Press,
2009, 557.
97. Zhu, HB, Liu, ZC and Xie, ZK et al. Synthesis and catalytic performances of
mesoporous zeolites templated by polyvinyl butyral gel as the mesopore di-
recting agent. J Phys Chem C 2008; 112: 17257–64.
98. Zhang, B, Wang, ZD and Ji, P et al. Efficient liquid-phase ethylation of benzene
with ethylene over mesoporous MCM-22 catalyst. Microporous Mesoporous
Mater 2013; 179: 63–8.
99. Yang, HQ, Liu, ZC and Xie, ZK et al. Transalkylation of diisopropylbenzenes with
benzene over hierarchical beta zeolite. Appl Catal A 2010; 379: 166–71.
100. Zhou, J, Liu, ZC and Xie, ZK et al. Enhanced accessibility and utilization effi-
ciency of acid sites in hierarchical MFI zeolite catalyst for effective diffusivity
improvement. RSC Adv 2014; 4: 43752–5.
101. Hua, ZL, Zhou, J and Shi, JL. Recent advances in hierarchically structured zeo-
lites: synthesis and material performances. Chem Commun 2011; 47: 10536–
47.
102. Chen, LH, Li, XY and Tang, Y et al. Hierarchically structured zeolites: synthesis,
masstransport properties and applications. J Mater Chem 2012; 22: 17381–
403.
103. Liu, FJ, Willhammar, T and Xiao, FS et al. ZSM-5 zeolite single crystals with
b-axis-aligned mesoporous channels as an efficient catalyst for conversion of
bulky organic molecules. J Am Chem Soc 2012; 134: 4557–60.
104. Pérez-Ramı́rez, J, Christensen, CH and Egeblad, K et al. Hierarchical zeolites:
enhanced utilisation of microporous crystals in catalysis by advances in mate-
rials design. Chem Soc Rev 2008; 37: 2530–42.
105. Jacobson, RH, Zhang, XJ and DuBose, RF et al. Three-dimensional structure
of beta-galactosidase from E. coli. Nature 1994; 369: 761–6.
106. Caplan, NA, Hancock, FE and Bulman, PC et al. Heterogeneous enantioselec-
tive catalyzed carbonyl- and imino-ene reactions using copper bis(oxazoline)
zeolite Y. Angew Chem In Ed 2004; 43: 1685–8.
107. Chen, ZJ, Guan, ZH and Li, MR et al. Enhancement of the performance of a
platinum nanocatalyst confined within carbon nanotubes for asymmetric hy-
drogenation. Angew Chem In Ed 2011; 50: 4913–7.
108. Li, B, Bai, SY and Wang, XF et al. Sustained water oxidation by a catalyst cage-
isolated in a metal-organic framework. Angew Chem In Ed 2012; 51: 11517–21.
 182 Natl Sci Rev, 2015, Vol. 2, No. 2
109. Li, J, Gao, S and Li, M et al. Influence of composition of heteropolyphospha-
totungstate catalyst on epoxidation of propylene. J Mol Catal A 2004; 218:
247–52.
110. Xie, ZK. Porous Catalytic Materials with New Structure and Improved Perfor-
mance. Beijing: Sinopec Press, 2010.
111. Xing, WH, Wang, Y and Chen, RZ et al. Membranes and membrane reactors:
state of the art, challenges, and opportunities. Sci China Chem 2014; 44: 1469–
80.
112. Zhong, ZX, Xing, WH and Liu, X et al. Fouling and regeneration of ceramic mem-
branes used in recovering titanium silicalite-1 catalysts. J Membr Sci 2007;
301: 67–75.
113. Lu, CJ, Chen, RZ and Xing, WH et al. A submerged membrane reactor for con-
tinuous phenol hydroxylation over TS-1. AIChE J 2008; 54: 1842–9.
114. Li, ZH, Chen, RZ and Xing, WH et al. Continuous acetone ammoximation over
TS-1 in a tubular membrane reactor. Ind Eng Chem Res 2010; 49: 6309–16.
115. Mapes, JE and Eischens, RP. The infrared spectra of ammonia chemisorbed
on cracking catalysts. J Phys Chem 1954; 58: 1059–62.
116. Buurmans, ILC and Weckhuysen, BM. Heterogeneities of individual catalyst
particles in space and time as monitored by spectroscopy. Nat Chem 2012; 4:
873–86.
117. Beale, AM, Jacques, SDM and Weckhuysen, BM. Chemical imaging of cat-
alytic solids with synchrotron radiation. Chem Soc Rev 2010; 39: 4656–72.
118. Groot, FMFD, Smit, ED and Schooneveld, MMV et al. In-situ scanning trans-
mission X-ray microscopy of catalytic solids and related nanomaterials. Chem
Phys Chem 2010; 11: 951–62.
Downloaded from https://academic.oup.com/nsr/article-abstract/2/2/167/2097218
by guest
on 21 February 2018
REVIEW
119. Fan, FT, Feng, ZC and Li, C et al. In situ UV Raman spectroscopic study on
the synthesis mechanism of AlPO-5. Angew Chem Int Ed 2009; 46: 8899–
903.
120. Fan, FT, Feng, ZC and Li, C. UV Raman spectroscopic study on the synthesis
mechanism and assembly of molecular sieves. Chem Soc Rev 2010; 39: 4794–
801.
121. Fan, FT, Feng, ZC and Li, C. UV Raman spectroscopic studies on active sites and
synthesis mechanisms of transition metal-containing microporous and meso-
porous materials. Acc Chem Res 2010; 43: 378–87.
122. Wang, JY, Fan, FT and Li, C et al. Influence of extra-framework Al on
the structure of the active iron sites in Fe/ZSM-35. J Catal 2013; 300:
251–9.
123. Pan, X and Bao, XH. The effects of confinement inside carbon nanotubes on
catalysis. Acc Chem Res 2011; 44: 553–62.
124. Zhang, F, Pan, XL and Hu, YF et al. Tuning the redox activity of encapsulated
metal clusters via the metallic and semiconducting character of carbon nan-
otubes. Proc Natl Acad Sci USA 2013; 110: 14861–6.
125. Fu, Q, Li, WX and Yao, YX et al. Interface-confined ferrous centers for catalytic
oxidation. Science 2010; 328: 1141–4.
126. Fu, G, Yi, XD and Huang, CJ. Developing selective oxidation catalysts of light
alkanes: from fundamental understanding to rational design. Surf Rev Lett
2007; 14: 645–56.
127. Wang, ML, Zheng, HZ and Li, JM et al. In situ Raman and pulse reaction study
on the partial oxidation of methane to synthesis gas over a Pt/Al2 O3 catalyst.
Chem-Asian J 2011; 6: 580–9.