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Vol. 14 (2022)

MOF-Transformed In2O3-x@C Nanocorn Electrocatalyst for Efficient CO2 Reduction to HCOOH

https://doi.org/10.1007/s40820-022-00913-6
Chen Qiu
Guangdong Key Lab of Nano‑Micro Material Research, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, People’s Republic of China
Kun Qian
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USA
Jun Yu
Guangdong Key Lab of Nano‑Micro Material Research, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, People’s Republic of China
Mingzi Sun
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong SAR, People’s Republic of China
Shoufu Cao
School of Materials Science and Engineering, China University of Petroleum, Qingdao, Shandong 266580, People’s Republic of China
Jinqiang Gao
Guangdong Key Lab of Nano‑Micro Material Research, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, People’s Republic of China
Rongxing Yu
Guangdong Key Lab of Nano‑Micro Material Research, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, People’s Republic of China
Lingzhe Fang
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USA
Youwei Yao
Shenzhen International Graduate School, Tsinghua University, Shenzhen, People’s Republic of China
Xiaoqing Lu
School of Materials Science and Engineering, China University of Petroleum, Qingdao, Shandong 266580, People’s Republic of China
Tao Li
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USA
Bolong Huang
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong SAR, People’s Republic of China
Shihe Yang
Guangdong Key Lab of Nano‑Micro Material Research, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, People’s Republic of China

Corresponding Author: Shihe Yang

chsyang@pku.edu.cn

Nano-Micro Letters, Vol. 14 (2022), Article Number: 167

Abstract

For electrochemical CO2 reduction to HCOOH, an ongoing challenge is to design energy efficient electrocatalysts that can deliver a high HCOOH current density (JHCOOH) at a low overpotential. Indium oxide is good HCOOH production catalyst but with low conductivity. In this work, we report a unique corn design of In2O3-x@C nanocatalyst, wherein In2O3-x nanocube as the fine grains dispersed uniformly on the carbon nanorod cob, resulting in the enhanced conductivity. Excellent performance is achieved with 84% Faradaic efficiency (FE) and 11 mA cm−2 JHCOOH at a low potential of − 0.4 V versus RHE. At the current density of 100 mA cm−2, the applied potential remained stable for more than 120 h with the FE above 90%. Density functional theory calculations reveal that the abundant oxygen vacancy in In2O3-x has exposed more In3+ sites with activated electroactivity, which facilitates the formation of HCOO* intermediate. Operando X-ray absorption spectroscopy also confirms In3+ as the active site and the key intermediate of HCOO* during the process of CO2 reduction to HCOOH.


Highlights:


1 The nanocorn design enables In2O3-x@C a high Faradaic efficiency of 98% and a high formate current density of 320 mA cm−2 at a low potential of -1.2 V versus hydrogen electrode without iR correction.
2 The rich O vacancy activates In3+ sites on the nanocube shell of In2O3-x@C and the carbon cob enhances conductivity.
3 Operando X-ray absorption spectroscopy unveils the active site of In3+ for formate production although reduction of In3+ to In is conceivable at the applied negative potentials during CO2 reduction reaction.

Keywords

CO2 reduction Indium oxide Formate Corn design Active sites
Qiu, Chen, Kun Qian, Jun Yu, Mingzi Sun, Shoufu Cao, Jinqiang Gao, Rongxing Yu, Lingzhe Fang, Youwei Yao, Xiaoqing Lu, Tao Li, Bolong Huang, and Shihe Yang. 2022. “MOF-Transformed In2O3-x@C Nanocorn Electrocatalyst for Efficient CO2 Reduction to HCOOH”. Nano-Micro Letters 14 (August):167. https://doi.org/10.1007/s40820-022-00913-6.
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References
  1. A. Wagner, C.D. Sahm, E. Reisner, Towards molecular understanding of local chemical environment effects in electro- and photocatalytic CO2 reduction. Nat. Catal. 3(10), 775–786 (2020). https://doi.org/10.1038/s41929-020-00512-x
  2. F. Pan, Y. Yang, Designing CO2 reduction electrode materials by morphology and interface engineering. Energy Environ. Sci. 13(8), 2275–2309 (2020). https://doi.org/10.1039/d0ee00900h
  3. M.B. Ross, P.D. Luna, Y. Li, C.T. Dinh, D. Kim et al., Designing materials for electrochemical carbon dioxide recycling. Nat. Catal. 2(8), 648–658 (2019). https://doi.org/10.1038/s41929-019-0306-7
  4. C. Chen, J.F.K. Kotyk, S.W. Sheehan, Progress toward commercial application of electrochemical carbon dioxide reduction. Chem 4(11), 2571–2586 (2018). https://doi.org/10.1016/j.chempr.2018.08.019
  5. X. Zhang, Y. Wang, M. Gu, M. Wang, Z. Zhang et al., Molecular engineering of dispersed nickel phthalocyanines on carbon nanotubes for selective CO2 reduction. Nat. Energy 5(9), 684–692 (2020). https://doi.org/10.1038/s41560-020-0667-9
  6. J. Li, S.U. Abbas, H. Wang, Z. Zhang, W. Hu, Recent advances in interface engineering for electrocatalytic CO2 reduction reaction. Nano-Micro Lett. 13, 216 (2021). https://doi.org/10.1007/s40820-021-00738-9
  7. D. Xue, H. Xia, W. Yan, J. Zhang, S. Mu, Defect engineering on carbon-based catalysts for electrocatalytic CO2 reduction. Nano-Micro Lett. 13, 5 (2020). https://doi.org/10.1007/s40820-020-00538-7
  8. N. Wang, R.K. Miao, G. Lee, A. Vomiero, D. Sinton, Suppressing the liquid product crossover in electrochemical CO2 reduction. SmartMat 2(1), 12–16 (2021). https://doi.org/10.1002/smm2.1018
  9. N. Han, P. Ding, L. He, Y.Y. Li, Y.G. Li, Promises of main group metal–based nanostructured materials for electrochemical CO2 reduction to formate. Adv. Energy Mater. 10(11), 1902338 (2019). https://doi.org/10.1002/aenm.201902338
  10. X. Zu, X. Li, W. Liu, Y. Sun, J. Xu et al., Efficient and robust carbon dioxide electroreduction enabled by atomically dispersed Snδ+ sites. Adv. Mater. 31(15), e1808135 (2019). https://doi.org/10.1002/adma.201808135
  11. J. Li, M. Zhu, Y.F. Han, Recent advances in electrochemical CO2 reduction on indium-based catalysts. ChemCatChem 13(2), 514–531 (2020). https://doi.org/10.1002/cctc.202001350
  12. Y.Y. Birdja, R.E. Vos, T.A. Wezendonk, L. Jiang, F. Kapteijn et al., Effects of substrate and polymer encapsulation on CO2 electroreduction by immobilized indium(III) protoporphyrin. ACS Catal. 8(5), 4420–4428 (2018). https://doi.org/10.1021/acscatal.7b03386
  13. I. Grigioni, L.K. Sagar, Y.C. Li, G. Lee, Y. Yan et al., CO2 electroreduction to formate at a partial current density of 930 mA cm–2 with inp colloidal quantum dot derived catalysts. ACS Energy Lett. 6(1), 79–84 (2020). https://doi.org/10.1021/acsenergylett.0c02165
  14. Z. Wang, Y. Zhou, C. Xia, W. Guo, B. You et al., Efficient electroconversion of carbon dioxide to formate by a reconstructed amino-functionalized indium-organic framework electrocatalyst. Angew. Chem. Int. Ed. 60(35), 19107–19112 (2021). https://doi.org/10.1002/anie.202107523
  15. J. Zhang, R. Yin, Q. Shao, T. Zhu, X. Huang, Oxygen vacancies in amorphous InOx nanoribbons enhance CO2 adsorption and activation for CO2 electroreduction. Angew. Chem. Int. Ed. 58(17), 5609–5613 (2019). https://doi.org/10.1002/anie.201900167
  16. X. Kang, B. Wang, K. Hu, K. Lyu, X. Han et al., Quantitative electro-reduction of CO2 to liquid fuel over electro-synthesized metal-organic frameworks. J. Am. Chem. Soc. 142(41), 17384–17392 (2020). https://doi.org/10.1021/jacs.0c05913
  17. Z. Zhang, F. Ahmad, W. Zhao, W. Yan, W. Zhang et al., Enhanced electrocatalytic reduction of CO2 via chemical coupling between indium oxide and reduced graphene oxide. Nano Lett. 19(6), 4029–4034 (2019). https://doi.org/10.1021/acs.nanolett.9b01393
  18. A. Dutta, I.Z. Montiel, K. Kiran, A. Rieder, V. Grozovski et al., A tandem (Bi2O3 → Bimet) catalyst for highly efficient ec-CO2 conversion into formate: operando raman spectroscopic evidence for a reaction pathway change. ACS Catal. 11(9), 4988–5003 (2021). https://doi.org/10.1021/acscatal.0c05317
  19. P. Deng, F. Yang, Z. Wang, S. Chen, Y. Zhou et al., Metal-organic framework-derived carbon nanorods encapsulating bismuth oxides for rapid and selective CO2 electroreduction to formate. Angew. Chem. Int. Ed. 59(27), 10807–10813 (2020). https://doi.org/10.1002/anie.202000657
  20. D. Wu, G. Huo, W. Chen, X.Z. Fu, J.L. Luo, Boosting formate production at high current density from CO2 electroreduction on defect-rich hierarchical mesoporous Bi/Bi2O3 junction nanosheets. Appl. Catal. B Enivron. 271, 118957 (2020). https://doi.org/10.1016/j.apcatb.2020.118957
  21. Q. Gong, P. Ding, M. Xu, X. Zhu, M. Wang et al., Structural defects on converted bismuth oxide nanotubes enable highly active electrocatalysis of carbon dioxide reduction. Nat. Commun. 10, 2807 (2019). https://doi.org/10.1038/s41467-019-10819-4
  22. J. Zou, C.Y. Lee, G.G. Wallace, Boosting formate production from CO2 at high current densities over a wide electrochemical potential window on a SnS catalyst. Adv. Sci. 8(15), e2004521 (2021). https://doi.org/10.1002/advs.202004521
  23. H.Q. Fu, J. Liu, N.M. Bedford, Y. Wang, J. Wright et al., Operando converting BiOCl into Bi2O2(CO3)xCly for efficient electrocatalytic reduction of carbon dioxide to formate. Nano-Micro Lett. 14, 121 (2022). https://doi.org/10.1007/s40820-022-00862-0
  24. D. Wu, R. Feng, C. Xu, P.F. Sui, J. Zhang et al., Regulating the electron localization of metallic bismuth for boosting CO2 electroreduction. Nano-Micro Lett. 14, 38 (2021). https://doi.org/10.1007/s40820-021-00772-7
  25. Y. Qi, L. Song, S. Ouyang, X. Liang, S. Ning et al., Photoinduced defect engineering: enhanced photothermal catalytic performance of 2D black In2O3-x nanosheets with bifunctional oxygen vacancies. Adv. Mater. 32(6), e1903915 (2020). https://doi.org/10.1002/adma.201903915
  26. J. Yu, J. Wang, X. Long, L. Chen, Q. Cao et al., Formation of feooh nanosheets induces substitutional doping of CeO2−x with high-valence Ni for efficient water oxidation. Adv. Energy Mater. 11(4), 2002731 (2021). https://doi.org/10.1002/aenm.202002731
  27. J. Yu, Z. Wang, J. Wang, W. Zhong, M. Ju et al., The role of ceria in a hybrid catalyst toward alkaline water oxidation. Chemsuschem 13(19), 5273–5279 (2020). https://doi.org/10.1002/cssc.202001542
  28. J. Yu, X. Du, H. Liu, C. Qiu, R. Yu et al., Mini review on active sites in Ce-based electrocatalysts for alkaline water splitting. Energy Fuels 35(23), 19000–19011 (2021). https://doi.org/10.1021/acs.energyfuels.1c02087
  29. S.M. Li, H. Duan, J. Yu, C. Qiu, R.X. Yu, Y.P. Chen, Y.P. Fang, X. Cai, S.H. Yang, Cu Vacancy induced product switching from formate to CO for CO2 reduction on copper sulfide. ACS Catal. 12(XXX), 9074–9082 (2020). https://doi.org/10.1021/acscatal.2c01750
  30. Y. Liang, W. Zhou, Y. Shi, C. Liu, B. Zhang, Unveiling in situ evolved In/In2O3− heterostructure as the active phase of In2O3 toward efficient electroreduction of CO2 to formate. Sci. Bull. 65(18), 1547–1554 (2020). https://doi.org/10.1016/j.scib.2020.04.022
  31. Y.F. Cui, W. Jiang, S. Liang, L.F. Zhu, Y.W. Yao, MOF-derived synthesis of mesoporous In/Ga oxides and their ultra-sensitive ethanol-sensing properties. J. Mater. Chem. A 6(30), 14930–14938 (2018). https://doi.org/10.1039/c8ta00269j
  32. B. Ravel, M. Newville, ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Rad. 12, 537–541 (2005). https://doi.org/10.1107/S0909049505012719
  33. S.J. Clark, M.D. Segall, C.J. Pickard, P.J. Hasnip, M.J. Probert et al., First principles methods using castep. Z. Kristallogr. Cryst. Mater. 220(5–6), 567–570 (2005). https://doi.org/10.1524/zkri.220.5.567.65075
  34. J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple. Phys. Rev. Lett. 77(18), 3865–3868 (1996). https://doi.org/10.1103/PhysRevLett.77.3865
  35. P.J. Hasnip, C.J. Pickard, Electronic energy minimisation with ultrasoft pseudopotentials. Comput. Phys. Commun. 174(1), 24–29 (2006). https://doi.org/10.1016/j.cpc.2005.07.011
  36. J.P. Perdew, J.A. Chevary, S.H. Vosko, K.A. Jackson, M.R. Pederson et al., Atoms, molecules, solids, and surfaces: applications of the generalized gradient approximation for exchange and correlation. Phys. Rev. B 46(11), 6671–6687 (1992). https://doi.org/10.1103/PhysRevB.46.6671
  37. J.D. Head, M.C. Zerner, A broyden—fletcher—goldfarb—shanno optimization procedure for molecular geometries. Chem. Phys. Lett. 122(3), 264–270 (1985). https://doi.org/10.1016/0009-2614(85)80574-1
  38. Z. Cai, J. Dai, W. Li, K.B. Tan, Z. Huang et al., Pd supported on MIL-68(In)-derived In2O3 nanotubes as superior catalysts to boost CO2 hydrogenation to methanol. ACS Catal. 10(22), 13275–13289 (2020). https://doi.org/10.1021/acscatal.0c03372
  39. Y. Qi, J. Jiang, X. Liang, S. Ouyang, W. Mi et al., Fabrication of black In2O3 with dense oxygen vacancy through dual functional carbon doping for enhancing photothermal CO2 hydrogenation. Adv. Funct. Mater. 31(22), 2100908 (2021). https://doi.org/10.1002/adfm.202100908
  40. J. Yu, Q. Cao, Y. Li, X. Long, S. Yang et al., Defect-rich niceox electrocatalyst with ultrahigh stability and low overpotential for water oxidation. ACS Catal. 9(2), 1605–1611 (2019). https://doi.org/10.1021/acscatal.9b00191
  41. W. Luo, W. Xie, M. Li, J. Zhang, A. Züttel, 3D hierarchical porous indium catalyst for highly efficient electroreduction of CO2. J. Mater. Chem. A 7(9), 4505–4515 (2019). https://doi.org/10.1039/c8ta11645h
  42. M. Zhu, P. Tian, J. Li, J. Chen, J. Xu et al., Structure-tunable copper-indium catalysts for highly selective CO2 electroreduction to CO or HCOOH. Chemsuschem 12(17), 3955–3959 (2019). https://doi.org/10.1002/cssc.201901884
  43. X. Sun, L. Lu, Q. Zhu, C. Wu, D. Yang et al., MoP nanops supported on indium-doped porous carbon: Outstanding catalysts for highly efficient CO2 electroreduction. Angew. Chem. Int. Ed. 57(9), 2427–2431 (2018). https://doi.org/10.1002/anie.201712221
  44. S. Liu, X.F. Lu, J. Xiao, X. Wang, X.W.D. Lou, Bi2O3 nanosheets grown on multi-channel carbon matrix to catalyze efficient CO2 electroreduction to HCOOH. Angew. Chem. Int. Ed. 58(39), 13828–13833 (2019). https://doi.org/10.1002/anie.201907674
  45. L. Yi, J. Chen, P. Shao, J. Huang, X. Peng et al., Molten-salt-assisted synthesis of bismuth nanosheets for long-term continuous electrocatalytic conversion of CO2 to formate. Angew. Chem. Int. Ed. 59(45), 20112–20119 (2020). https://doi.org/10.1002/anie.202008316
  46. F. Li, G.H. Gu, C. Choi, P. Kolla, S. Hong et al., Highly stable two-dimensional bismuth metal-organic frameworks for efficient electrochemical reduction of CO2. Appl. Catal. B 277, 119241 (2020). https://doi.org/10.1016/j.apcatb.2020.119241
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