Citation: Du Ying, Shen Yang-Bin, Zhan Yu-Lu, Ning Fan-Di, Yan Liu-Ming, Zhou Xiao-Chun. Highly active iridium catalyst for hydrogen production from formic acid[J]. Chinese Chemical Letters, ;2017, 28(8): 1746-1750. doi: 10.1016/j.cclet.2017.05.018 shu

Highly active iridium catalyst for hydrogen production from formic acid

Du Ying ^a,b ,
Shen Yang-Bin ^b,c ,
Zhan Yu-Lu ^a,b ,
Ning Fan-Di ^b,d ,
Yan Liu-Ming ^a ,
Zhou Xiao-Chun ^b,,

a.
Department of Chemistry, Shanghai University, Shanghai 200444, China
b.
Division of Advanced Nanomaterials, Suzhou Institute of Nano-tech and Nano-bionics, Chinese Academy of Sciences, Suzhou 215125, China
c.
University of Chinese Academy of Sciences, Beijing 100049, China
d.
University of Science and Technology of China, Hefei 230026, China

Corresponding author: Zhou Xiao-Chun, xczhou2013@sinano.ac.cn
Received Date: 7 February 2017
Revised Date: 23 March 2017
Accepted Date: 27 April 2017
Available Online: 20 August 2017

Figures(6)

Formic acid (FA) dehydrogenation has attracted a lot of attentions since it is a convenient method for H₂ production. In this work, we designed a self-supporting fuel cell system, in which H₂ from FA is supplied into the fuel cell, and the exhaust heat from the fuel cell supported the FA dehydrogenation. In order to realize the system, we synthesized a highly active and selective homogeneous catalyst IrCp^*Cl₂bpym for FA dehydrogenation. The turnover frequency (TOF) of the catalyst for FA dehydrogenation is as high as 7150 h^-1 at 50 ℃, and is up to 144, 000 h^-1 at 90 ℃. The catalyst also shows excellent catalytic stability for FA dehydrogenation after several cycles of test. The conversion ratio of FA can achieve 93.2%, and no carbon monoxide is detected in the evolved gas. Therefore, the evolved gas could be applied in the proton exchange membrane fuel cell (PEMFC) directly. This is a potential technology for hydrogen storage and generation. The power density of the PEMFC driven by the evolved gas could approximate to that using pure hydrogen.
- Formic acid,
- Hydrogen generation,
- Homogeneous catalyst,
- Catalytic performance,
- Proton exchange membrane fuel cell
1. [1]
  Zhu Q.L., Xu Q.. Liquid organic and inorganic chemical hydrides for highcapacity hydrogen storage[J]. Energy Environ. Sci., 2015,8:478-512. doi: 10.1039/C4EE03690E
2. [2]
  Yadav M., Xu Q.. Liquid-phase chemical hydrogen storage materials[J]. Energy Environ. Sci., 2012,5:9698-9725. doi: 10.1039/c2ee22937d
3. [3]
  Grasemann M., Laurenczy G.. Formic acid as a hydrogen source-recent developments and future trends[J]. Energy Environ. Sci., 2012,5:8171-8181. doi: 10.1039/c2ee21928j
4. [4]
  Fellay C., Dyson P.J., Laurenczy G.. A viable hydrogen-storage system based on selective formic acid decomposition with a ruthenium catalyst[J]. Angew. Chem. Int. Ed., 2008,120:4030-4032. doi: 10.1002/(ISSN)1521-3757
5. [5]
  Johnson T.C., Morris D.J., Wills M.. Hydrogen generation from formic acid and alcohols using homogeneous catalysts[J]. Chem. Soc. Rev., 2010,39:81-88. doi: 10.1039/B904495G
6. [6]
  Gu X., Lu Z.H., Jiang H.L., Akita T., Xu Q.. Synergistic catalysis of metal-organic framework-immobilized Au-Pd nanoparticles in dehydrogenation of formic acid for chemical hydrogen storage[J]. J. Am. Chem. Soc., 2011,133:11822-11825. doi: 10.1021/ja200122f
7. [7]
  Fukuzumi S., Kobayashi T., Suenobu T.. Efficient catalytic decomposition of formic acid for the selective generation of H₂ and H/D exchange with a watersoluble rhodium complex in aqueous solution[J]. ChemSusChem, 2008,1:827-834. doi: 10.1002/cssc.v1:10
8. [8]
  Himeda Y.. Highly efficient hydrogen evolution by decomposition of formic acid using an iridium catalyst with 4, 4'-dihydroxy-2, 2'-bipyridine[J]. Green Chem., 2009,11:2018-2022. doi: 10.1039/b914442k
9. [9]
  Singh A.K., Jang S., Kim J.Y.. One-pot defunctionalization of lignin-derived compounds by dual-functional Pd₅₀Ag₅₀/Fe₃O₄/N-rGO Catalyst[J]. ACS Catal., 2015,5:6964-6972. doi: 10.1021/acscatal.5b01319
10. [10]
  Sponholz P., Mellmann D., Junge H., Beller M.. Towards a practical setup for hydrogen production from formic acid[J]. ChemSusChem, 2013,6:1172-1176. doi: 10.1002/cssc.201300186
11. [11]
  Tedsree K., Li T., Jones S.. Hydrogen production from formic acid decomposition at room temperature using a Ag-Pd core-shell nanocatalyst[J]. Nat. Nanotechnol., 2011,6:302-307. doi: 10.1038/nnano.2011.42
12. [12]
  Wu S., Yang F., Wang H.. Mg²⁺-assisted low temperature reduction of alloyed AuPd/C:an efficient catalyst for hydrogen generation from formic acid at room temperature[J]. Chem. Commun., 2015,51:10887-10890. doi: 10.1039/C5CC02604K
13. [13]
  Yan J.M., Wang Z.L., Gu L.. AuPd-MnOx/MOF-Graphene:An Efficient Catalyst for Hydrogen Production from Formic Acid at Room Temperature[J]. Adv.Energy Mater., 2015,51500107. doi: 10.1002/aenm.201500107
14. [14]
  Zhang S., Metin O., Su D., Sun S.. Monodisperse AgPd alloy nanoparticles and their superior catalysis for the dehydrogenation of formic acid[J]. Angew. Chem. Int. Ed., 2013,52:3681-3684. doi: 10.1002/anie.201300276
15. [15]
  Bavykina A.V., Goesten M.G., Kapteijn F., Makkee M., Gascon J.. Efficient production of hydrogen from formic acid using a covalent triazine framework supported molecular catalyst[J]. ChemSusChem, 2015,8:809-812. doi: 10.1002/cssc.v8.5
16. [16]
  Wang Z., Lu S.M., Li J., Wang J., Li C.. Unprecedentedly high formic acid dehydrogenation activity on an iridium complex with an N, N'-diimine ligand in water[J]. Chem.-Eur. J., 2015,21:12592-12595. doi: 10.1002/chem.201502086
17. [17]
  Hull J.F., Himeda Y., Wang W.H.. Reversible hydrogen storage using CO₂ and a proton-switchable iridium catalyst in aqueous media under mild temperatures and pressures[J]. Nat. Chem., 2012,4:383-388. doi: 10.1038/nchem.1295
18. [18]
  Boddien A., Gartner F., Jackstell R.. ortho-Metalation of iron(0) tribenzylphosphine complexes:homogeneous catalysts for the generation of hydrogen from formic acid[J]. Angew. Chem. Int. Ed., 2010,49:8993-8996. doi: 10.1002/anie.v49.47
19. [19]
  Fukuzumi S., Kobayashi T., Suenobu T.. Unusually large tunneling effect on highly efficient generation of hydrogen and hydrogen isotopes in pH-selective decomposition of formic acid catalyzed by a heterodinuclear iridiumruthenium complex in water[J]. J. Am. Chem. Soc., 2010,132:1496-1497. doi: 10.1021/ja910349w
20. [20]
  Jiang K., Xu K., Zou S., Cai W.B.. B-doped Pd catalyst:boosting roomtemperature hydrogen production from formic acid-formate solutions[J]. J. Am. Chem. Soc., 2014,136:4861-4864. doi: 10.1021/ja5008917
21. [21]
  Chen Y., Zhu Q.L., Tsumori N., Xu Q.. Immobilizing highly catalytically active noble metal nanoparticles on reduced graphene oxide:a non-noble metal sacrificial approach[J]. J. Am. Chem. Soc., 2015,137:106-109. doi: 10.1021/ja511511q
22. [22]
  Cai Y.Y., Li X.H., Zhang Y.N.. Highly efficient dehydrogenation of formic acid over a palladium-nanoparticle-based Mott-Schottky photocatalyst[J]. Angew. Chem. Int. Ed., 2013,52:11822-11825. doi: 10.1002/anie.v52.45
23. [23]
  Bi Q.Y., Du X.L., Liu Y.M.. Efficient subnanometric gold-catalyzed hydrogen generation via formic acid decomposition under ambient conditions[J]. J. Am. Chem. Soc., 2012,134:8926-8933. doi: 10.1021/ja301696e
24. [24]
  Wang Z.L., Yan J.M., Ping Y.. An efficient CoAuPd/C catalyst for hydrogen generation from formic acid at room temperature[J]. Angew. Chem. Int. Ed., 2013,52:4406-4409. doi: 10.1002/anie.201301009
25. [25]
  Yang L., Hua X., Su J.. Highly efficient hydrogen generation from formic acid-sodium formate over monodisperse AgPd nanoparticles at room temperature[J]. App. Catal. B:Environ., 2015,168-169:423-428. doi: 10.1016/j.apcatb.2015.01.003
26. [26]
  Yoo J.S., Zhao Z.J., Nørskov J.K., Studt F.. Effect of Boron Modifications of Palladium Catalysts for the Production of Hydrogen from Formic Acid[J]. ACS Catal., 2015,5:6579-6586. doi: 10.1021/acscatal.5b01497
27. [27]
  Qin Y.L., Liu Y.C., Liang F., Wang L.M.. Preparation of Pd-Co-based nanocatalysts and their superior applications in formic acid decomposition and methanol oxidation[J]. ChemSusChem, 2015,8:260-263. doi: 10.1002/cssc.201402926
28. [28]
  Li F.F., Gu J.N., Zhou X.C.. Single molecule electro-catalysis of non-fluorescent molecule[J]. Chin. Chem. Lett., 2015,26:1514-1517. doi: 10.1016/j.cclet.2015.09.013
29. [29]
  Wang Y.X., Chen T.H.. A high dispersed Pt0.35Pd0.35Co0.30/C as superior catalyst for methanol and formic acid electro-oxidation[J]. Chin. Chem. Lett., 2014,25:907-911. doi: 10.1016/j.cclet.2014.04.031
30. [30]
  Zhou X., Huang Y., Xing W.. High-quality hydrogen from the catalyzed decomposition of formic acid by Pd-Au/C and Pd-Ag/C[J]. Chem. Commun., 2008:3540-3542.
31. [31]
  Huang Y., Zhou X., Yin M., Liu C., Xing W.. Novel PdAu@Au/C Core-Shell Catalyst:Superior Activity and Selectivity in Formic Acid Decomposition for Hydrogen Generation[J]. Chem. Mater., 2010,22:5122-5128. doi: 10.1021/cm101285f
32. [32]
  Zhou X., Huang Y., Liu C.. Available hydrogen from formic acid decomposed by rare earth elements promoted Pd-Au/C catalysts at low temperature[J]. ChemSusChem, 2010,3:1379-1382. doi: 10.1002/cssc.201000199
33. [33]
  Wang W., He T., Liu X.. Highly active carbon supported Pd-Ag nanofacets catalysts for hydrogen production from HCOOH[J]. ACS Appl. Mater. Interfaces, 2016,8:20839-20848. doi: 10.1021/acsami.6b08091
34. [34]
  Ren M.J., Zhou Y., Tao F.F.. Controllable modification of the electronic structure of carbon-supported core-shell Cu@Pd catalysts for formic acid oxidation[J]. J. Phys. Chem. C, 2014,118:12669-12675. doi: 10.1021/jp5033417
35. [35]
  Ren M., Kang Y., He W.. Origin of performance degradation of palladiumbased direct formic acid fuel cells[J]. App. Catal. B-Environ., 2011,104:49-53. doi: 10.1016/j.apcatb.2011.02.029
36. [36]
  Govindaswamy P., Canivet J., Therrien B.. Mono and dinuclear rhodium, iridium and ruthenium complexes containing chelating 2, 20-bipyrimidine ligands:Synthesis, molecular structure, electrochemistry and catalytic properties[J]. J. Organomet. Chem., 2007,692:3664-3675. doi: 10.1016/j.jorganchem.2007.04.048
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