DOI: 10.1002/slct.

201702863 Communications

1
2 z Catalysis
3
4
5
Formic Acid or Formate Derivatives as the In Situ
6 Hydrogen Source in Au-Catalyzed Reduction of
7
8 para-Chloronitrobenzene
9
10 Zhun Hu,*[a] Shunquan Tan,[a] Rongli Mi,[a] Xiang Li,[a] Jing Bai,[a] Xiaoyan Guo,[a]
11 Guoyang Hu,[a] Peng Hang,[a] Juan Li,[a] Dan Li,[a] Yang Yang,[c] and Xianghui Yan[b]
12
13
Formic acid and formate derivatives as hydrogen source on the Formic acid (FA) is considered as one of the most promising
14
hydrogenation of para-chloronitrobenzene (p-CNB) over sup- materials for hydrogen storage today. Expediently, FA is a
15
ported gold catalysts were investigated. The hydrogenation kinetically stable liquid at room temperature and has a hydro-
16
activity in various formate derivatives followed the order: gen content of 4.4 wt%, being a liquid hydrogen carrier.
17
HCOOH < HCOONa < HCOOK < HCOONH4, which was in Besides, FA is an important intermediate, by-product and
18
accordance with the decrement of electronegativity of cation product in the chemical industry as well as a major product in
19
species in formate derivatives. Moreover, in the case of biomass processes (fermentation). Moreover, the use of formic
20
HCOONH4 as hydrogen source, the p-CNB conversion could acid is very atom efficient since 100% of the stored hydrogen is
21
enhance ten-fold as the hydrogen source of H2 at 60 oC. This available for catalytic cycle, compare to the percentage of H2
22
promotion effect was also found in other supported Au stored in methanol (66%) and methane (50%). Formic acid or
23
catalysts. These results provide a general alternative hydrogen formate derivatives could be decomposed into H2 and CO2 by
24
source to replace conventional H2 as reducing agent for fine noble metal catalysts, which makes it in situ H2 source for the
25
chemical processes. enhancement of H2 utilization efficiency in various reactions. It
26
had been reported that Au catalyst show superior activity on
27
the decomposition of HCOOH. Furthermore, Au catalyst owning
28
high selectivity hydrogenation of para-chloronitrobenzene,
29
compared to other precious metal, have attracted much
30 Introduction
attention.[15–19] Thus, it is of interest to examine the catalytic
31
Hydrogenation reaction is a vital branch of the value-added hydrogenation of para-chloronitrobenzene over Au catalyst
32
product in the chemical engineering process, which often using with HCOOH or formate derivatives as the reducing agent
33
an external H2 supply.[1–4] However the use of H2 in the catalytic precursor.
34
reduction of para-chloronitrobenzene may cause problems, In this work, we firstly investigated the hydrogenation of
35
especially when regarding its potential for industrial applica- para-chloronitrobenzene over Au/ZrO2 catalyst with formic acid
36
tions. Large amounts of H2 were wasted in this process and or formic derivatives as hydrogen source. The hydrogenation
37
could be released into the environment, which not only activity over Au/ZrO2 catalyst with HCOONH4 as hydrogen
38
increased the cost of the operation but also posed a contingent source could enhance 3 ~ 11 times compared with H2 at the
39
danger of explosion. Much efforts have been paid on the varied reaction temperature (60 ~ 150 oC). Then Au catalyst
40
exploit substituent hydrogen source for hydrogen gas to supported other oxides (Al2O3, CeO2, TiO2, SiO2), exhibited
41
achieve high activity and selectivity.[5–14] similar superior activity with HCOONH4 as hydrogen source.
42
These findings provided a substituted hydrogen source to
43
replace H2 on the hydrogenation reaction over supported Au
44
catalyst.
45 [a] Dr. Z. Hu, S. Tan, R. Mi, X. Li, J. Bai, X. Guo, G. Hu, P. Hang, J. Li, D. Li
46 Institute of Industrial Catalysis, School of Chemical Engineering and
47 Technology, Results and discussion
Xi’an Jiaotong University
48 Xi’an Shaanxi 710049, China Table 1 shows hydrogenation activity of p-CNB over Au/ZrO2
49 E-mail: huzhun@mail.xjtu.edu.cn
catalyst with varied hydrogen sources. Au/ZrO2 catalyst was
50 [b] Dr. X. Yan
School of Materials Science and Engineering firstly chosen to investigate the effect of hydrogen source on
51
North Minzu University the hydrogenation of p-CNB, since Au/ZrO2 was reported as
52 Yinchuan 750021, China high performance on the hydrogenation of p-CNB[20–23] and
53 [c] Y. Yang
dehydrogenation of HCOOH.[9,10] When H2 was used as hydro-
54 Sinochem Morden Environmental Protection Chemicals (Xi’an) Co., LTD
Xi’an Shaanxi 710049, China gen source, p-CNB conversion over Au/ZrO2 catalyst was 25.0%.
55
Supporting information for this article is available on the WWW under However, replacing H2 with HCOOH, nearly no reaction
56
https://doi.org/10.1002/slct.201702863 occurred and the p-CNB hydrogenation conversion decreased
57

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Table 1. Catalytic results of the selective hydrogenation of p-CNB over Au/ hydrogen source in the hydrogenation reaction, whereas NH4 +
1
ZrO2 with varied hydrogen sources[a] was as a promoter, since the hydrogen atom in NH3*H2O was
2
Hydrogen Temp. Product sel. (%)
inadequate to p-CNB complete conversion in hydrogenation
3
source (oC) Conv. (%) p-CAN AN NB reaction. Au catalysts were often restricted with H2 activation in
4
previous reports,[1,4,24,25] resulting in much efforts have paid on
5 H2 150 25.0 99.4 0.6 0.0
HCOOH 150 0.6 82.8 4.5 12.6
the enhancement of H2 activation via additional of other
6
HCOONa 150 2.1 89.7 10.3 0.0 precious metals (Pt,[21,22] Pd[26]) or increasing reaction temper-
7
HCOOK 150 53.5 74.3 12.0 13.8 ature. Thereby, lower reaction temperatures have been inves-
8 HCOONH4 150 > 99.9 99.2 0.8 0.0 tigated at the hydrogen source of HCOONH4, since p-CNB was
9 HCOOH + NH3·H2O 150 > 99.9 98.9 0.0 1.1
completely conversion at 150 oC.
10
[a] Reaction conditions: 25.0 mg catalyst, 1.0 mmol p-CNB, 1 mmol o-xylene Table 2 shows the catalytic activity over Au/ZrO2 with H2 or
11 in 5 mL ethanol, 150 oC, 2.0 MPa H2, 1 h, stirring speed: 900 rpm.
HCOONH4 as hydrogen source with varied reaction temper-
12
ature. The p-CNB conversion increased from 3.8% to 6.9%,
13
19.7% and 25.0%, with H2 as hydrogen source, when the
14
dramatically to 0.6%. Further other formate derivatives (HCOO- reaction temperature was raised from 60 oC to 90, 120 oC and
15
Na, HCOOK, HCOONH4) was substituted to H2 as hydrogen 150 oC. Moreover, the desired product p-CAN selectivity
16
source, p-CNB conversion increased from 0.6% to 2.1%, 53.5% increased with increment of reaction temperature. Whereas, in
17
and 100%, when hydrogen source was shifted from HCOOH to the case of HCOONH4 as hydrogen source, the p-CNB
18
HCOONa, HCOOK and HCOONH4, respectively. In order to conversion was 48% at 60 oC. Further increasing the reaction
19
comprehend the hydrogen atom from NH4 + or HCOO to temperature to 90, 120, 150 oC, it is surprising that p-CNB could
20
hydrogenation of p-CNB, 4 mmol HCOOH and 1 mmol NH3*H2O be completely converted. Meanwhile, the p-CAN selectivity in
21
were added to investigate the hydrogenation of p-CNB. It the condition of HCOONH4 as hydrogen source exhibited
22
should be noted that p-CNB was nearly completely converted similar orderliness with H2 as hydrogen source with increment
23
to p-CAN. These results indicated that HCOOH was as the of reaction temperature. It should be noted that the activity of
24
p-CNB hydrogenation in the case of HCOONH4 as hydrogen
25
source was enhanced ca. 13 times at lower than 90 oC,
26
compared with H2 as conventional reducing agent. This promo-
27 Table 2. Catalytic results of the selective hydrogenation of p-CNB over Au/
tional effect render the potential substitute hydrogen source to
28 ZrO2 with H2 and HCOONH4 as hydrogen source at varied reaction
temperatures.[a] replace H2 with HCOONH4.
29
In order to certify this promotional effect on the other
30 Hydrogen Temp. Product sel. (%)
source (oC) Conv. (%) p-CAN AN NB supported Au catalysts, Au/MOx (MOx = Al2O3, SiO2, TiO2, CeO2)
31
catalysts were investigated using H2 and HCOONH4 as hydro-
32 H2 60 3.8 71.9 28.1 0.0
gen sources at 150 oC. Table 3 shows the catalytic activity of p-
33 90 6.9 82.6 17.4 0.2
120 19.7 94.3 5.7 0.0 CNB hydrogenation over varied supported Au catalysts with H2
34
150 25.0 99.4 0.6 0.0 and HCOONH4 as hydrogen sources. In contrast with H2, all the
35
supported Au catalysts presented much superior catalytic
36 HCOONH4 60 48.0 77.4 21.4 1.3
activity in the HCOONH4 as hydrogen source. The p-CAN
37 90 > 99.9 78.7 21.0 0.3
120 > 99.9 98.1 1.8 0.1 selectivity remained indistinguishable in these two reducing
38
150 > 99.9 99.2 0.8 0.0 agent. For the Au/TiO2, Au/CeO2 and Au/Al2O3 catalysts, p-CNB
39
[a] Reaction conditions: 25.0 mg catalyst, 1.0 mmol p-CNB, 1 mmol o-xylene
could be entirely converted and p-CAN selectivity was above
40
in 5 mL ethanol, 2.0 MPa H2, 1 h, stirring speed: 900 rpm. 99% in the case of HCOONH4 as hydrogen source. These results
41
42
43
Table 3. Catalytic results of the selective hydrogenation of p-CNB over varied supported Au catalysts with H2 and HCOONH4 as hydrogen source at 150 oC.[a]
44
45 Hydrogen Product sel. (%)
Catalyst source Conv. (%) p-CAN AN NB
46
[b]
47 Au/SiO2 H2 3.2 86.8 13.2 0.0
48 HCOONH4 6.9 82.6 17.4 0.2
Au/TiO2 H2 85.8 100.0 0.0 0.0
49
HCOONH4 99.3 99.6 0.1 0.3
50 Au/CeO2 H2 22.6 100.0 0.0 0.0
51 HCOONH4 99.0 98.6 1.4 0.0
52 Au/ZrO2 H2 25.0 99.4 0.6 0.0
HCOONH4 > 99.9 99.2 0.8 0.0
53
Au/Al2O3 H2 27.8 99.0 0.8 0.2
54 HCOONH4 > 99.9 99.1 0.0 0.9
55
[a] Reaction conditions: 25.0 mg catalyst, 1.0 mmol p-CNB, 1 mmol o-xylene in 5 mL ethanol, 150 oC, 2.0 MPa H2 or 4 mmol HCOONH4, 1 h, stirring speed:
56 900 rpm. [b] Reaction time 4 h.
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demonstrated that HCOONH4 could be as a potential hydrogen be increased ca. 13 times compared with H2 as hydrogen source
1
source with the replacement of H2 in the absence of modify p- at 60 oC. Further employing other supported Au catalysts in the
2
CAN selectivity. HCOONH4 as hydrogen source, all the supported Au catalysts
3
For the H2 as conventional hydrogen source, the reaction exhibited preferable activity compared with H2 as hydrogen
4
mechanism for the selective hydrogenation of p-CNB over Au source. These results provide a guideline to choose a substitute
5
catalyst was regarded as Langmuir-Hinshelwood mechanism.[27] hydrogen source on the heterogeneous Au catalysis, especially for
6
The rate determining step was conceived as the hydrogen clean energy storage/distribution and extended applications of
7
activation over Au surface. hydrogen dissociative adsorption on formate derivatives in fine chemical processes.
8
the metal surface and generates active H atoms, p-CNB also
9
adsorbed on the neighbouring active site, then H atom reacted
10 Supporting Information
with –NO2 or C Cl group of the adsorbed reactant molecule.
11
The reaction pathway was mainly hinged on the adsorption Supporting Information file includes details about sample
12
forms of H2 and the organic reactant on the metal surface, preparation and hydrogenation reaction.
13
which was often affected by the used solvent in the
14
heterogeneous reaction system. Much effort has been paid on
15 Acknowledgements
the enhancement of H2 activation via accession of precious
16
metal (Pt and Pd), resulting in the increment of cost.[21,22,26] Our We acknowledge the financial support from the China Postdoc-
17
results provided an alternative way to heighten the reaction toral Science Foundation (2017 M613143), the Fundamental
18
rate by means of HCOONH4 as hydrogen source. Research Funds for the Central Universities (xjj2016113), the Key
19
Therefore, a possible mechanism was proposed as shown in Research Project of North Minzu University (2015KJ20) and
20
Scheme 1. Formate derivatives first adsorbed on the Au surface, National Natural Science Foundation of China (U1662117).
21
22
23 Conflict of Interest
24
The authors declare no conflict of interest.
25
26
27 Keywords: Au catalyst · Formate derivatives · Formic acid ·
28 Hydrogen source · Hydrogenation reaction · para-
29 Chloronitrobenzene
30 Scheme 1. Adsorption of p-CNB and formate derivatives over supported Au
31 catalysts
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