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Research Article

Polysulfide modified PtCu intermetallic nanocatalyst with enrichment realizes efficient electrooxidation ethanol to CO2

Shuanglong Zhou1, Zheng Lv1, Liang Zhao1, Dan Zhang1, Zuocao Wang1, Yu Dai2, Bin Li3, Olga Starostenko4, Jianping Lai1( ), Lei Wang1,5( )
Key Laboratory of Eco-chemical Engineering, Ministry of Education, Taishan scholar advantage and characteristic discipline team of Eco-chemical process and technology, Laboratory of Inorganic Synthesis and Applied Chemistry, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
College of Foreign Languages, Qingdao City University, Qingdao 266106, China
College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
Institute of Macromolecular Chemistry of the National Academy of Sciences of Ukraine, Kyiv 02160, Ukraine
Shandong Engineering Research Center for Marine Environment Corrosion and Safety Protection, College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
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Graphical Abstract

A novel PtCu intermetallic/C modified by polysulfide electrocatalyst (S3.67-PtCu IM/C) for ethanol oxidation reaction (EOR) was designed. Benefiting from the polysulfide with enrichment and stabilizing effect, a large number of ethanol and hydroxyl species were enriched on the catalyst surface, boosting the cleavage of C–C bond and accelerating the oxidation of CO. The mass activity and specific activity reached 17.83 A·mgPt−1 and 24.67 mA·cm−2 in 1 M KOH. The CO2 selectivity achieved 93.5% at 0.6 V vs. reversible hydrogen electrode (RHE).

Abstract

The main problem faced by ethanol oxidation reaction (EOR) includes low activity, poor selectivity, and durability. In the study, we found that polysulfide modified on the surface of PtCu intermetallic (IM)/C can simultaneously enrich hydroxyl and ethanol, which could effectively improve the catalytic activity, CO2 selectivity, and durability of catalyst. The mass activity and the specific activity of the product in 1 M KOH electrolyte reached 17.83 A·mgPt−1 and 24.67 mA·cm−2. The CO2 selectivity of polysulfide modified product achieved 93.5%, which was 30 folds higher than Pt/C. In addition, the catalyst showed high catalytic stability. The mechanism study demonstrates that the surface modified polysulfide could significantly boost the enrichment effect of ethanol and hydroxyl species, accelerating C–C bond cleavage and CO oxidation.

Keywords

PtCO2 selectivityenrichment effectethanol oxidation reaction (EOR)electrocatalyst

Electronic Supplementary Material

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References

[1]

Badalyan, A.; Stahl, S. S. Cooperative electrocatalytic alcohol oxidation with electron–proton-transfer mediators. Nature 2016, 535, 406–410.
Crossref Google Scholar
[2]

Zeb Gul Sial, M. A.; Ud Din, M. A.; Wang, X. Multimetallic nanosheets: Synthesis and applications in fuel cells. Chem. Soc. Rev. 2018, 47, 6175–6200.
Crossref Google Scholar
[3]

Tang, C.; Zheng, Y.; Jaroniec, M.; Qiao, S. Z. Electrocatalytic refinery for sustainable production of fuels and chemicals. Angew. Chem., Int. Ed. 2021, 60, 19572–19590.
Crossref Google Scholar
[4]

Han, S. M.; He, C. H.; Yun, Q. B.; Li, M. Y.; Chen, W.; Cao, W. B.; Lu, Q. P. Pd-based intermetallic nanocrystals: From precise synthesis to electrocatalytic applications in fuel cells. Coord. Chem. Rev. 2021, 445, 214085.
Crossref Google Scholar
[5]

Wang, Y.; Zheng, X. B.; Wang, D. S. Design concept for electrocatalysts. Nano Res. 2022, 15, 1730–1752.
Crossref Google Scholar
[6]

Fang, Y.; Guo, S. Y.; Cao, D. J.; Zhang, G. L.; Wang, Q.; Chen, Y. Z.; Cui, P.; Cheng, S.; Zuo, W. S. Five-fold twinned Ir-alloyed Pt nanorods with high C1 pathway selectivity for ethanol electrooxidation. Nano Res. 2022, 15, 3933–3939.
Crossref Google Scholar
[7]

Bai, S. X.; Xu, Y.; Cao, K. L.; Huang, X. Q. Selective ethanol oxidation reaction at the Rh–SnO2 interface. Adv. Mater. 2021, 33, 2005767.
Crossref Google Scholar
[8]

Lv, F.; Zhang, W. Y.; Sun, M. Z.; Lin, F. X.; Wu, T.; Zhou, P.; Yang, W. X.; Gao, P.; Huang, B. L.; Guo, S. J. Au clusters on Pd nanosheets selectively switch the pathway of ethanol electrooxidation: Amorphous/crystalline interface matters. Adv. Energy Mater. 2021, 11, 2100187.
Crossref Google Scholar
[9]

Wang, Y.; Zheng, M.; Li, Y. R.; Ye, C. L.; Chen, J.; Ye, J. Y.; Zhang, Q. H.; Li, J.; Zhou, Z. Y.; Fu, X. Z. et al. p–d orbital hybridization induced by a monodispersed Ga site on a Pt3Mn nanocatalyst boosts ethanol electrooxidation. Angew. Chem., Int. Ed. 2022, 61, e202115735.
Crossref Google Scholar
[10]

Jiang, K. Z.; Wang, P. T.; Guo, S. J.; Zhang, X.; Shen, X.; Lu, G.; Su, D.; Huang, X. Q. Ordered PdCu-based nanoparticles as bifunctional oxygen-reduction and ethanol-oxidation electrocatalysts. Angew. Chem., Int. Ed. 2016, 55, 9030–9035.
Crossref Google Scholar
[11]

Li, S. P.; Lai, J. P.; Luque, R.; Xu, G. B. Designed multimetallic Pd nanosponges with enhanced electrocatalytic activity for ethylene glycol and glycerol oxidation. Energy Environ. Sci. 2016, 9, 3097–3102.
Crossref Google Scholar
[12]

Jia, Y. Y.; Jiang, Y. Q.; Zhang, J. W.; Zhang, L.; Chen, Q. L.; Xie, Z. X.; Zheng, L. S. Unique excavated rhombic dodecahedral PtCu3 alloy nanocrystals constructed with ultrathin nanosheets of high-energy {110} facets. J. Am. Chem. Soc. 2014, 136, 3748–3751.
Crossref Google Scholar
[13]

Ding, J. B.; Bu, L. Z.; Guo, S. J.; Zhao, Z. P.; Zhu, E. B.; Huang, Y.; Huang, X. Q. Morphology and phase controlled construction of Pt-Ni nanostructures for efficient electrocatalysis. Nano Lett. 2016, 16, 2762–2767.
Crossref Google Scholar
[14]

Li, M. X.; Cai, Y. D.; Zhang, J. J.; Sun, H. X.; Li, Z.; Liu, Y. J.; Zhang, X.; Dai, X. P.; Gao, F.; Song, W. Y. Highly stable Pt3Ni ultralong nanowires tailored with trace Mo for the ethanol oxidation. Nano Res. 2022, 15, 3230–3238.
Crossref Google Scholar
[15]

Huang, W. J.; Ma, X. Y.; Wang, H.; Feng, R. F.; Zhou, J. G.; Duchesne, P. N.; Zhang, P.; Chen, F. J.; Han, N.; Zhao, F. P. et al. Promoting effect of Ni(OH)2 on palladium nanocrystals leads to greatly improved operation durability for electrocatalytic ethanol oxidation in alkaline solution. Adv. Mater. 2017, 29, 1703057.
Crossref Google Scholar
[16]

Li, S. N.; Wang, Y.; Li, Y. R.; Fang, X.; Liu, Y. J.; Li, M. X.; Wang, Z.; Gao, Y. F.; Sun, H. X.; Gao, F. et al. PtNiCu nanowires with advantageous lattice-plane boundary for enhanced ethanol electrooxidation. Nano Res. 2022, 15, 2877–2886.
Crossref Google Scholar
[17]

Rodríguez-Gómez, A.; Dorado, F.; Sánchez, P.; De La Osa, A. R. Boosting hydrogen and chemicals production through ethanol electro-reforming on Pt-transition metal anodes. J. Energy Chem. 2022, 70, 394–406.
Crossref Google Scholar
[18]

Wang, K. L.; Wang, F.; Zhao, Y. F.; Zhang, W. Q. Surface-tailored PtPdCu ultrathin nanowires as advanced electrocatalysts for ethanol oxidation and oxygen reduction reaction in direct ethanol fuel cell. J. Energy Chem. 2021, 52, 251–261.
Crossref Google Scholar
[19]

Chen, J. Y.; Lim, S. C.; Kuo, C. H.; Tuan, H. Y. Sub-1 nm PtSn ultrathin sheet as an extraordinary electrocatalyst for methanol and ethanol oxidation reactions. J. Colloid Interface Sci. 2019, 545, 54–62.
Crossref Google Scholar
[20]

Kodiyath, R.; Ramesh, G. V.; Koudelkova, E.; Tanabe, T.; Ito, M.; Manikandan, M.; Ueda, S.; Fujita, T.; Umezawa, N.; Noguchi, H. et al. Promoted C–C bond cleavage over intermetallic TaPt3 catalyst toward low-temperature energy extraction from ethanol. Energy Environ. Sci. 2015, 8, 1685–1689.
Crossref Google Scholar
[21]

Dai, S.; Huang, T. H.; Yan, X. X.; Yang, C. Y.; Chen, T. Y.; Wang, J. H.; Pan, X. Q.; Wang, K. W. Promotion of ternary Pt-Sn-Ag catalysts toward ethanol oxidation reaction: Revealing electronic and structural effects of additive metals. ACS Energy Lett. 2018, 3, 2550–2557.
Crossref Google Scholar
[22]

Wang, K.; Du, H. Y.; Sriphathoorat, R.; Shen, P. K. Vertex-type engineering of Pt-Cu-Rh heterogeneous nanocages for highly efficient ethanol electrooxidation. Adv. Mater. 2018, 30, 1804074.
Crossref Google Scholar
[23]

Tian, H.; Zhu, R.; Deng, P.; Li, J.; Huang, W.; Chen, Q.; Su, Y.; Jia, C.; Liu, Z.; Shen, Y. et al. Ultrathin Pd3Pt1Rh0.1 nanorings with strong C–C bond breaking ability for the ethanol oxidation reaction. Small 2022, 18, 2203506.
Crossref Google Scholar
[24]

Li, J. R.; Jilani, S. Z.; Lin, H. H.; Liu, X. M.; Wei, K. C.; Jia, Y. K.; Zhang, P.; Chi, M. F.; Tong, Y. J.; Xi, Z. et al. Ternary CoPtAu nanoparticles as a general catalyst for highly efficient electro-oxidation of liquid fuels. Angew. Chem., Int. Ed. 2019, 58, 11527–11533.
Crossref Google Scholar
[25]

Bai, J.; Liu, D. Y.; Yang, J.; Chen, Y. Nanocatalysts for electrocatalytic oxidation of ethanol. ChemSusChem 2019, 12, 2117–2132.
Crossref Google Scholar
[26]

Liang, Z. X.; Song, L.; Deng, S. Q.; Zhu, Y. M.; Stavitski, E.; Adzic, R. R.; Chen, J. Y.; Wang, J. X. Direct 12-electron oxidation of ethanol on a ternary Au (core)–PtIr (shell) electrocatalyst. J. Am. Chem. Soc. 2019, 141, 9629–9636.
Crossref Google Scholar
[27]

Casado-Rivera, E.; Volpe, D. J.; Alden, L.; Lind, C.; Downie, C.; Vázquez-Alvarez, T.; Angelo, A. C. D.; DiSalvo, F. J.; Abruña, H. D. Electrocatalytic activity of ordered intermetallic phases for fuel cell applications. J. Am. Chem. Soc. 2004, 126, 4043–4049.
Crossref Google Scholar
[28]

Shi, Y. D.; Liao, F.; Zhu, W. X.; Shi, H. X.; Yin, K.; Shao, M. W. Carbon dots promote the performance of anodized nickel passivation film on ethanol oxidation by enhancing oxidation of the intermediate. Chin. J. Chem. 2021, 39, 1199–1204.
Crossref Google Scholar
[29]

Lv, H.; Lopes, A.; Xu, D. D.; Liu, B. Multimetallic hollow mesoporous nanospheres with synergistically structural and compositional effects for highly efficient ethanol electrooxidation. ACS Cent. Sci. 2018, 4, 1412–1419.
Crossref Google Scholar
[30]

He, Q. G.; Shyam, B.; Macounová, K.; Krtil, P.; Ramaker, D.; Mukerjee, S. Dramatically enhanced cleavage of the C–C bond using an electrocatalytically coupled reaction. J. Am. Chem. Soc. 2012, 134, 8655–8661.
Crossref Google Scholar
[31]

Zhu, Y. M.; Bu, L. Z.; Shao, Q.; Huang, X. Q. Structurally ordered Pt3Sn nanofibers with highlighted antipoisoning property as efficient ethanol oxidation electrocatalysts. ACS Catal. 2020, 10, 3455–3461.
Crossref Google Scholar
[32]

Luo, A. P.; Zhang, L.; Liao, Y. J.; Li, L. X.; Yang, Q.; Wu, X. T.; Wu, X. Y.; He, D. S.; He, C. Y.; Chen, W. et al. A tensile-strained Pt-Rh single-atom alloy remarkably boosts ethanol oxidation. Adv. Mater. 2021, 33, 2008508.
Crossref Google Scholar
[33]

Ji, X. L.; Lee, K. T.; Holden, R.; Zhang, L.; Zhang, J. J.; Botton, G. A.; Couillard, M.; Nazar, L. F. Nanocrystalline intermetallics on mesoporous carbon for direct formic acid fuel cell anodes. Nat. Chem. 2010, 2, 286–293.
Crossref Google Scholar
[34]

Zhao, X. R.; Cheng, H.; Song, L.; Han, L. L.; Zhang, R.; Kwon, G.; Ma, L.; Ehrlich, S. N.; Frenkel, A. I.; Yang, J. et al. Rhombohedral ordered intermetallic nanocatalyst boosts the oxygen reduction reaction. ACS Catal. 2021, 11, 184–192.
Crossref Google Scholar
[35]

Luo, L. H.; Wang, M. L.; Cui, Y.; Chen, Z. Y.; Wu, J. X.; Cao, Y. L.; Luo, J.; Dai, Y. Z.; Li, W. X.; Bao, J. et al. Surface iron species in palladium-iron intermetallic nanocrystals that promote and stabilize CO2 methanation. Angew. Chem. 2020, 132, 14542–14550.
Crossref Google Scholar
[36]

Xie, X. F.; Zhang, Z. H.; Chen, Z. K.; Wu, J. Y.; Li, Z. L.; Zhong, S. P.; Liu, H.; Xu, Z. F.; Liu, Z. L. In-situ preparation of zinc sulfide adsorbent using local materials for elemental mercury immobilization and recovery from zinc smelting flue gas. Chem. Eng. J. 2022, 429, 132115.
Crossref Google Scholar
[37]

Hui, L.; Zhang, X. T.; Xue, Y. R.; Chen, X.; Fang, Y.; Xing, C. Y.; Liu, Y. X.; Zheng, X. C.; Du, Y. C.; Zhang, C. et al. Highly dispersed platinum chlorine atoms anchored on gold quantum dots for a highly efficient electrocatalyst. J. Am. Chem. Soc. 2022, 144, 1921–1928.
Crossref Google Scholar
[38]

Chen, C.; Zhu, Y. Z.; Tian, M.; Chen, Y.; Yang, Y. J.; Jiang, K.; Gao, S. Y. Sustainable self-powered electro-Fenton degradation using N,S co-doped porous carbon catalyst fabricated with adsorption–pyrolysis–doping strategy. Nano Energy 2021, 81, 105623.
Crossref Google Scholar
[39]

Xiao, L. P.; Li, G.; Yang, Z.; Chen, K.; Zhou, R. S.; Liao, H. G.; Xu, Q. C.; Xu, J. Engineering of amorphous PtOx interface on Pt/WO3 nanosheets for ethanol oxidation electrocatalysis. Adv. Funct. Mater. 2021, 31, 2100982.
Crossref Google Scholar
[40]

Bach Delpeuch, A.; Maillard, F.; Chatenet, M.; Soudant, P.; Cremers, C. Ethanol oxidation reaction (EOR) investigation on Pt/C, Rh/C, and Pt-based bi- and tri-metallic electrocatalysts: A DEMS and in situ FTIR study. Appl. Catal. B: Environ. 2016, 181, 672–680.
Crossref Google Scholar
[41]

Qin, Y. N.; Huang, H.; Yu, W. H.; Zhang, H. N.; Li, Z. J.; Wang, Z. C.; Lai, J. P.; Wang, L.; Feng, S. H. Porous PdWM (M = Nb, Mo and Ta) trimetallene for high C1 selectivity in alkaline ethanol oxidation reaction. Adv. Sci. 2022, 9, 2103722.
Crossref Google Scholar
[42]

Li, M.; Cullen, D. A.; Sasaki, K.; Marinkovic, N. S.; More, K.; Adzic, R. R. Ternary electrocatalysts for oxidizing ethanol to carbon dioxide: Making Ir capable of splitting C–C bond. J. Am. Chem. Soc. 2013, 135, 132–141.
Crossref Google Scholar
[43]

Peng, H. C.; Ren, J.; Wang, Y. C.; Xiong, Y.; Wang, Q. C.; Li, Q.; Zhao, X.; Zhan, L. S.; Zheng, L. R.; Tang, Y. G. et al. One-stone, two birds: Alloying effect and surface defects induced by Pt on Cu2−xSe nanowires to boost C–C bond cleavage for electrocatalytic ethanol oxidation. Nano Energy 2021, 88, 106307.
Crossref Google Scholar
[44]

Shen, C.; Chen, H. M.; Qiu, M. Y.; Shi, Y. Q.; Yan, W.; Jiang, Q. R.; Jiang, Y. Q.; Xie, Z. X. Introducing oxophilic metal and interstitial hydrogen into the Pd lattice to boost electrochemical performance for alkaline ethanol oxidation. J. Mater. Chem. A 2022, 10, 1735–1741.
Crossref Google Scholar
[45]

Jiang, Z.; Zhang, Q.; Liang, Z. X.; Chen, J. G. Pt-modified TaC as an efficient electrocatalyst for ethanol oxidation in acid and alkaline electrolytes. Appl. Catal. B: Environ. 2018, 234, 329–336.
Crossref Google Scholar
[46]

Li, M. G.; Zhao, Z. L.; Zhang, W. Y.; Luo, M. C.; Tao, L.; Sun, Y. J.; Xia, Z. H.; Chao, Y. G.; Yin, K.; Zhang, Q. H. et al. Sub-monolayer YOx/MoOx on ultrathin Pt nanowires boosts alcohol oxidation electrocatalysis. Adv. Mater. 2021, 33, 2103762.
Crossref Google Scholar
[47]

Lan, B.; Wang, Q. L.; Ma, Z. X.; Wu, Y. J.; Jiang, X. L.; Jia, W. S.; Zhou, C. X.; Yang, Y. Y. Efficient electrochemical ethanol-to-CO2 conversion at rhodium and bismuth hydroxide interfaces. Appl. Catal. B: Environ. 2022, 300, 120728.
Crossref Google Scholar
[48]

Dong, J. C.; Zhang, X. G.; Briega-Martos, V.; Jin, X.; Yang, J.; Chen, S.; Yang, Z. L.; Wu, D. Y.; Feliu, J. M.; Williams, C. T. et al. In situ Raman spectroscopic evidence for oxygen reduction reaction intermediates at platinum single-crystal surfaces. Nat. Energy 2018, 4, 60–67.
Crossref Google Scholar
[49]

Li, S.; Guan, A. X.; Wang, H. N.; Yan, Y. Q.; Huang, H. L.; Jing, C.; Zhang, L. J.; Zhang, L. J.; Zheng, G. F. Hybrid palladium nanoparticles and nickel single atom catalysts for efficient electrocatalytic ethanol oxidation. J. Mater. Chem. A 2022, 10, 6129–6133.
Crossref Google Scholar
[50]

Han, S. H.; Liu, H. M.; Chen, P.; Jiang, J. X.; Chen, Y. Porous trimetallic PtRhCu cubic nanoboxes for ethanol electrooxidation. Adv. Energy Mater. 2018, 8, 1801326.
Crossref Google Scholar
Nano Research
Volume 17 Issue 4,
April 2024
Pages 2320-2327
DOI: 10.1007/s12274-023-6043-x
Cite this article:
Zhou S, Lv Z, Zhao L, et al. Polysulfide modified PtCu intermetallic nanocatalyst with enrichment realizes efficient electrooxidation ethanol to CO2. Nano Research, 2024, 17(4): 2320-2327. https://doi.org/10.1007/s12274-023-6043-x
Topics:
Electrocatalysis

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Received: 13 June 2023
Revised: 21 July 2023
Accepted: 26 July 2023
Published: 23 August 2023
© Tsinghua University Press 2023
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