Methanol electro-oxidation to formate on iron-substituted lanthanum cobaltite perovskite oxides

Meng Fanxu; Dai Chencheng; Liu Zheng; Luo Songzhu; Ge Jingjie; Duan Yan; Chen Gao; Wei Chao; Chen Riccardo Ruixi; Wang Jiarui; Mandler Daniel; Xu Zhichuan J.

doi:10.1016/j.esci.2022.02.001

Volume 2 Issue 1

Jan. 2022

Turn off MathJax

Article Contents

Article Navigation > eScience > 2022 > 2(1): 87-94

Meng Fanxu, Dai Chencheng, Liu Zheng, Luo Songzhu, Ge Jingjie, Duan Yan, Chen Gao, Wei Chao, Chen Riccardo Ruixi, Wang Jiarui, Mandler Daniel, Xu Zhichuan J.. Methanol electro-oxidation to formate on iron-substituted lanthanum cobaltite perovskite oxides[J]. eScience, 2022, 2(1): 87-94. doi: 10.1016/j.esci.2022.02.001

Citation:

Meng Fanxu, Dai Chencheng, Liu Zheng, Luo Songzhu, Ge Jingjie, Duan Yan, Chen Gao, Wei Chao, Chen Riccardo Ruixi, Wang Jiarui, Mandler Daniel, Xu Zhichuan J.. Methanol electro-oxidation to formate on iron-substituted lanthanum cobaltite perovskite oxides[J]. eScience, 2022, 2(1): 87-94. doi: 10.1016/j.esci.2022.02.001

Citation:

Meng Fanxu, Dai Chencheng, Liu Zheng, Luo Songzhu, Ge Jingjie, Duan Yan, Chen Gao, Wei Chao, Chen Riccardo Ruixi, Wang Jiarui, Mandler Daniel, Xu Zhichuan J.. Methanol electro-oxidation to formate on iron-substituted lanthanum cobaltite perovskite oxides[J]. eScience, 2022, 2(1): 87-94. doi: 10.1016/j.esci.2022.02.001

PDF( 0 KB)

Methanol electro-oxidation to formate on iron-substituted lanthanum cobaltite perovskite oxides

doi: 10.1016/j.esci.2022.02.001

Meng Fanxu^{a, c, 1},
Dai Chencheng^{a, 1},
Liu Zheng^a,
Luo Songzhu^a,
Ge Jingjie^a,
Duan Yan^{a, b},
Chen Gao^a,
Wei Chao^a,
Chen Riccardo Ruixi^{a, b},
Wang Jiarui^{a, c},
Mandler Daniel^{c, d
,
,},
Xu Zhichuan J.^{a, b, c
,
,}

a.
School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang, Avenue, Singapore, 639798, Singapore
b.
Energy Research Institute @NTU ERI@N, Interdisciplinary Graduate School, Technological University, Nanyang, Singapore, 639798, Singapore
c.
Singapore-HUJ Alliance for Research and Enterprise, NEW-CREATE Phase II, Campus for Research Excellence and Technological Enterprise (CREATE), Singapore, 138602, Singapore
d.
Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem, 9190401, Israel

More Information

Corresponding author: Daniel Mandler Daniel.Mandler@mail.huji.ac.il; Zhichuan J. Xu xuzc@ntu.edu.sg
Received Date: 2021-07-29
Revised Date: 2021-12-17
Accepted Date: 2022-02-03

Available Online: 2022-02-11

Abstract

Abstract

Electrochemically producing formate by oxidizing methanol is a promising way to add value to methanol. Noble metal-based electrocatalysts, which have been extensively studied for the methanol oxidation reaction, can catalyze the complete oxidation of methanol to carbon dioxide, but not the mild oxidation to formate. As a result, exploring efficient and earth-abundant electrocatalysts for formate production from methanol is of interest. Herein, we present the electro-oxidation of methanol to formate, catalyzed by iron-substituted lanthanum cobaltite (LaCo₁_−xFe_xO₃). The Fe/Co ratio in the oxides greatly influences the activity and selectivity. This effect is attributed to the higher affinity of Fe and Co to the two reactants: CH₃OH and OH⁻, respectively. Because a balance between these affinities is favored, LaCo_0.5Fe_0.5O₃ shows the highest formate production rate, at 24.5 mmol h⁻¹ g_oxide⁻¹, and a relatively high Faradaic efficiency of 44.4% in a series of (LaCo₁_−xFe_xO₃) samples (x = 0.00, 0.25, 0.50, 0.75, 1.00) at 1.6 V versus a reversible hydrogen electrode.
- Methanol,
- Electro-oxidation,
- Formate,
- Oxides,
- Perovskite

● Electro-oxidation of methanol to formate is catalyzed by iron substituted lanthanum cobaltite (LaCo₁_−xFe_xO₃).
● (LaCo_0.5Fe_0.5O₃) shows the highest formate production rate of 24.5 mmol h⁻¹ g_oxide⁻¹ and a relatively high Faradaic efficiency of 44.4%.
● DFT calculations revealed the influence of iron substitution on the activity and selectivity.
● The Fe/Co ratio in the oxides greatly influences the activity and selectivity.
¹ These authors contributed equally to this work.

FullText(HTML)

Supplements(1)

eScience-2-1-87.docx

References(44)

References

[1]	D. A. Bulushev, J. R. H. Ross, Towards sustainable production of formic acid, ChemSusChem 11 (2018) 821-836 doi: 10.1002/cssc.201702075
[2]	I. A. Zolotarskii, T. V. Andrushkevich, G. Y. Popova, S. Stompel, V. O. Efimov, V. B. Nakrokhin, L. Y. Zudilina, N. V. Vernikovskaya, Modeling, design and operation of pilot plant for two-stage oxidation of methanol into formic acid, Chem. Eng. J. 238 (2014) 111-119 doi: 10.1016/j.cej.2013.08.026
[3]	J. Hietala, A. Vuori, P. Johnsson, I. Pollari, W. Reutemann, H. Kieczka, Formic acid, in: B. Elvers, C. Ley (Eds.), Ullmann's Encyclopedia of Industrial Chemistry, 2016, pp. 1-22
[4]	C. Fellay, P. J. Dyson, G. Laurenczy, A viable hydrogen-storage system based on selective formic acid decomposition with a ruthenium catalyst, Angew. Chem. Int. Ed. 47 (2008) 3966-3968 doi: 10.1002/anie.200800320
[5]	F. Joo, A breakthrough in sustainable production of formate salts: combined catalytic methanol dehydrogenation and bicarbonate hydrogenation, ChemCatChem 6 (2014) 3306-3308 doi: 10.1002/cctc.201402591
[6]	T. V. Andrushkevich, G. Y. Popova, E. V. Danilevich, I. A. Zolotarskii, V. B. Nakrokhin, T. A. Nikoro, S. I. Stompel, V. N. Parmon, A new gas-phase method for formic acid production: tests on a pilot plant, Catalys. Indus. 6 (2014) 17-24 doi: 10.1134/S2070050414010024
[7]	Z. Pi, H. Zhong, Integrating hydrogen production with selective methanol oxidation to value-added formate over a NiS bifunctional electrocatalyst, IOP Conf. Ser. Earth Environ. Sci. 651 (2021) 042062 doi: 10.1088/1755-1315/651/4/042062
[8]	X. Han, H. Sheng, C. Yu, T. W. Walker, G. W. Huber, J. Qiu, S. Jin, Electrocatalytic oxidation of glycerol to formic acid by CuCo2O4 spinel oxide nanostructure catalysts, ACS Catal. 10 (2020) 6741-6752 doi: 10.1021/acscatal.0c01498
[9]	C. Dong, X. Zong, W. Jiang, L. Niu, Z. Liu, D. Qu, X. Wang, Z. Sun, Recent advances of ceria-based materials in the oxidation of carbon monoxide, Small Struct. 2 (2021) 2000081 doi: 10.1002/sstr.202000081
[10]	L. Zhang, H. Zhao, S. Xu, Q. Liu, T. Li, Y. Luo, S. Gao, X. Shi, A. M. Asiri, X. Sun, Recent advances in 1D electrospun nanocatalysts for electrochemical water splitting, Small Struct. 2 (2021) 2000048 doi: 10.1002/sstr.202000048
[11]	S. S. Mahapatra, J. Datta, Characterization of Pt-Pd/C electrocatalyst for methanol oxidation in alkaline medium, Intern. J. Electrochem. 2011 (2011) 1-16 doi: 10.4061/2011/563495
[12]	M. V. Pagliaro, M. Bellini, J. Filippi, M. G. Folliero, A. Marchionni, H. A. Miller, W. Oberhauser, F. Vizza, Hydrogen production from the electrooxidation of methanol and potassium formate in alkaline media on carbon supported Rh and Pd nanoparticles, Inorg. Chim. Acta. 470 (2018) 263-269 doi: 10.1016/j.ica.2017.05.055
[13]	D. Y. Chung, K.-J. Lee, Y.-E. Sung, Methanol electro-oxidation on the Pt surface: revisiting the cyclic voltammetry interpretation, J. Phys. Chem. C 120 (2016) 9028-9035 doi: 10.1021/acs.jpcc.5b12303
[14]	W. Huang, H. Wang, J. Zhou, J. Wang, P. N. Duchesne, D. Muir, P. Zhang, N. Han, F. Zhao, M. Zeng, J. Zhong, C. Jin, Y. Li, S. T. Lee, H. Dai, Highly active and durable methanol oxidation electrocatalyst based on the synergy of platinum-nickel hydroxide-graphene, Nat. Commun. 6 (2015) 10035 doi: 10.1038/ncomms10035
[15]	S. W. Lee, S. Chen, W. Sheng, N. Yabuuchi, Y.-T. Kim, T. Mitani, E. Vescovo, Y. Shao-Horn, Roles of surface steps on Pt nanoparticles in electro-oxidation of carbon monoxide and methanol, J. Am. Chem. Soc. 131 (2009) 15669-15677 doi: 10.1021/ja9025648
[16]	J. Suntivich, Z. Xu, C. E. Carlton, J. Kim, B. Han, S. W. Lee, N. Bonnet, N. Marzari, L. F. Allard, H. A. Gasteiger, K. Hamad-Schifferli, Y. Shao-Horn, Surface composition tuning of Au-Pt bimetallic nanoparticles for enhanced carbon monoxide and methanol electro-oxidation, J. Am. Chem. Soc. 135 (2013) 7985-7991 doi: 10.1021/ja402072r
[17]	K. Miecznikowski, WO3 decorated carbon nanotube supported PtSn nanoparticles with enhanced activity towards electrochemical oxidation of ethylene glycol in direct alcohol fuel cells, Arab. J. Chem. 13 (2020) 1020-1031 doi: 10.1016/j.arabjc.2017.09.005
[18]	Y.-W. Zhou, Y.-F. Chen, K. Jiang, Z. Liu, Z.-J. Mao, W.-Y. Zhang, W.-F. Lin, W.-B. Cai, Probing the enhanced methanol electrooxidation mechanism on platinum-metal oxide catalyst, Appl. Catal. B Environ. 280 (2021) doi: 10.1016/j.apcatb.2020.119393
[19]	J. Mateos-Santiago, M. L. Hernandez-Pichardo, L. Lartundo-Rojas, A. Manzo-Robledo, Methanol electro-oxidation on Pt-carbon vulcan catalyst modified with WOx nanostructures: an approach to the reaction sequence using DEMS, Ind. Eng. Chem. Res. 56 (2016) 161-167
[20]	K. Zhang, W. Yang, C. Ma, Y. Wang, C. Sun, Y. Chen, P. Duchesne, J. Zhou, J. Wang, Y. Hu, M. N. Banis, P. Zhang, F. Li, J. Li, L. Chen, A highly active, stable and synergistic Pt nanoparticles/Mo2C nanotube catalyst for methanol electro-oxidation, NPG Asia Mater. 7 (2015) e153-e153
[21]	H. A. Gasteiger, N. Markovic, P. N. Ross, E. J. Cairns, Methanol electrooxidation on well-characterized platinum-ruthenium bulk alloys, J. Phys. Chem. 97 (1993) 12020-12029 doi: 10.1021/j100148a030
[22]	A. G. Hubert, M. Nenad, N. R. Philip, J. C. Elton, Temperature-dependent methanol electro-oxidation on well-characterized Pt-Ru alloys, J. Electrochem. Soc. 141 (1994) 1795-1803 doi: 10.1149/1.2055007
[23]	L. Yaqoob, T. Noor, N. Iqbal, Recent progress in development of efficient electrocatalyst for methanol oxidation reaction in direct methanol fuel cell, Int. J. Energy Res. 45 (2020) 6550-6583
[24]	A. Yuda, A. Ashok, A. Kumar, A comprehensive and critical review on recent progress in anode catalyst for methanol oxidation reaction, Catal. Rev. (2020) 1-103
[25]	S. Rezaee, S. Shahrokhian, Facile synthesis of petal-like NiCo/NiO-CoO/nanoporous carbon composite based on mixed-metallic MOFs and their application for electrocatalytic oxidation of methanol, Appl. Catal. B Environ. 244 (2019) 802-813 doi: 10.1016/j.apcatb.2018.12.013
[26]	M. Li, X. Deng, K. Xiang, Y. Liang, B. Zhao, J. Hao, J. L. Luo, X. Z. Fu, Value-Added formate production from selective methanol oxidation as anodic reaction to enhance electrochemical hydrogen cogeneration, ChemSusChem 13 (2020) 914-921 doi: 10.1002/cssc.201902921
[27]	K. Xiang, D. Wu, X. Deng, M. Li, S. Chen, P. Hao, X. Guo, J. L. Luo, X. Z. Fu, Boosting H2 generation coupled with selective oxidation of methanol into value-added chemical over cobalt Hydroxide@Hydroxysulfide nanosheets electrocatalysts, Adv. Funct. Mater. 30 (2020) doi: 10.1002/adfm.201909610
[28]	C. Liu, W. Zhou, J. Zhang, Z. Chen, S. Liu, Y. Zhang, J. Yang, L. Xu, W. Hu, Y. Chen, Y. Deng, Air-assisted transient synthesis of metastable nickel oxide boosting alkaline fuel oxidation reaction, Adv. Energy Mater. 10 (2020) doi: 10.1002/aenm.202001397
[29]	B. Miao, Z.-P. Wu, H. Xu, M. Zhang, Y. Chen, L. Wang, DFT studies on the key competing reaction steps towards complete ethanol oxidation on transition metal catalysts, Comput. Mater. Sci. 156 (2019) 175-186 doi: 10.1016/j.commatsci.2018.09.029
[30]	J. Hao, J. Liu, D. Wu, M. Chen, Y. Liang, Q. Wang, L. Wang, X.-Z. Fu, J.-L. Luo, In situ facile fabrication of Ni(OH)2 nanosheet arrays for electrocatalytic co-production of formate and hydrogen from methanol in alkaline solution, Appl. Catal. B Environ. 281 (2021)
[31]	J. Li, R. Wei, X. Wang, Y. Zuo, X. Han, J. Arbiol, J. Llorca, Y. Yang, A. Cabot, C. Cui, Selective methanol-to-formate electrocatalytic conversion on branched nickel carbide, Angew Chem. Int. Ed. Engl. 59 (2020) 20826-20830 doi: 10.1002/anie.202004301
[32]	J. Lv, W. Feng, S. Yang, H. Liu, X. Huang, Methanol dissociation and oxidation on single Fe atom supported on graphitic carbon nitride, Appl. Organomet. Chem. 33 (2019)
[33]	J. Li, C. Xing, Y. Zhang, T. Zhang, M. C. Spadaro, Q. Wu, Y. Yi, S. He, J. Llorca, J. Arbiol, A. Cabot, C. Cui, Nickel iron diselenide for highly efficient and selective electrocatalytic conversion of methanol to formate, Small 17 (2021) e2006623 doi: 10.1002/smll.202006623
[34]	Y. Duan, S. Sun, S. Xi, X. Ren, Y. Zhou, G. Zhang, H. Yang, Y. Du, Z. J. Xu, Tailoring the Co 3d-O 2p covalency in LaCoO3 by Fe substitution to promote oxygen evolution reaction, Chem. Mater. 29 (2017) 10534-10541 doi: 10.1021/acs.chemmater.7b04534
[35]	M. Wang, B. Han, J. Deng, Y. Jiang, M. Zhou, M. Lucero, Y. Wang, Y. Chen, Z. Yang, A. T. N'Diaye, Q. Wang, Z. J. Xu, Z. Feng, Influence of Fe substitution into LaCoO3 electrocatalysts on oxygen-reduction activity, ACS Appl. Mater. Interfaces 11 (2019) 5682-5686 doi: 10.1021/acsami.8b20780
[36]	M. Sivakumar, M. Sakthivel, S.-M. Chen, P. Veerakumar, S.-B. Liu, Sol-gel synthesis of carbon-coated LaCoO3 for effective electrocatalytic oxidation of salicylic acid, Chemelectrochem 4 (2017) 935-940 doi: 10.1002/celc.201600714
[37]	C. Sun, J. A. Alonso, J. Bian, Recent advances in perovskite-type oxides for energy conversion and storage applications, Adv. Energy Mater. 11 (2021) 2000459 doi: 10.1002/aenm.202000459
[38]	R. Shannon, Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides, Acta Crystallogr. A 32 (1976) 751-767 doi: 10.1107/S0567739476001551
[39]	H. Liang, Y. Hong, C. Zhu, S. Li, Y. Chen, Z. Liu, D. Ye, Influence of partial Mn-substitution on surface oxygen species of LaCoO3 catalysts, Catal. Today 201 (2013) 98-102 doi: 10.1016/j.cattod.2012.04.036
[40]	X. Li, H. Zhang, S. Li, W. Fan, M. Zhao, IR transmission spectra of nanocrystalline powder materials of the composite oxides La1 − xSrxFe1 − yCoyO3 with the perovskite structure, Mater. Chem. Phys. 41 (1995) 41-45 doi: 10.1016/0254-0584(95)01502-7
[41]	J. Y. Chang, B. N. Lin, Y. Y. Hsu, H. C. Ku, Co K-edge XANES and spin-state transition of RCoO3 (R=La, Eu), Phys. B Condens. Matter 329-333 (2003) 826-828
[42]	C. Wei, S. Sun, D. Mandler, X. Wang, S. Z. Qiao, Z. J. Xu, Approaches for measuring the surface areas of metal oxide electrocatalysts for determining their intrinsic electrocatalytic activity, Chem. Soc. Rev. 48 (2019) 2518-2534 doi: 10.1039/c8cs00848e
[43]	N. A. Karim, S. K. Kamarudin, L. K. Shyuan, Z. Yaakob, W. R. W. Daud, A. A. H. Khadum, Novel cathode catalyst for DMFC: study of the density of states of oxygen adsorption using density functional theory, Int. J. Hydrogen Energy 39 (2014) 17295-17305 doi: 10.1016/j.ijhydene.2014.06.110
[44]	C. Dai, Y. Sun, G. Chen, A. C. Fisher, Z. J. Xu, Electrochemical oxidation of nitrogen towards direct nitrate production on spinel oxides, Angew. Chem. Int. Ed. 59 (2020) 9418-9422 doi: 10.1002/anie.202002923