The C-C bond cleavage inhibition and intermediates adsorption enhancement co-boost the selective electrooxidation of ethylene glycol on silver-palladium hollow nanocubes

doi:10.1016/S1872-2067(26)65015-2

Abstract

Abstract:

Efficient electrooxidation of ethylene glycol (EG) to glycolic acid (GA) is highly desirable for biomass valorization and EG recycling, which remains challenging owing to side reactions involving C-C bond cleavage. Herein, the bimetallic AgPd hollow nanocubes (AgPd hNCs) are successfully prepared via a solvothermal-assisted Galvanic replacement strategy. Both theoretical calculations and experimental results indicate that the electronic interplay between the Pd atom and Ag atom hinders C-C bond breaking and enhances the adsorption of critical intermediates, resulting in high selectivity toward GA production. Benefiting from these features, AgPd hNCs achieve a Faradaic efficiency of 93% toward GA formation and a 2.8-fold increase in mass activity compared to Pd black. Moreover, the strong oxygen affinity of Ag promotes the removal of CO-like intermediates from the Pd surface, resulting in superior EG oxidation stability. This study highlights a generalizable Ag-based strategy to modulate bimetallic interfaces for selective oxidation reaction of specific functional groups, contributing to the rational design of electrocatalysts for biomass upgrading.

Key words: Ethylene glycol oxidation reaction, Hollow nanocubes, Electronic structure, Ag-Pd alloy, Selectivity

Zi-Hang Wang, Wei Zhong, Si-Qi Li, Bin Sun, Hao Lan, Xiao-Yu Zhang, Xin Wang, Yu Chen, Xuan Ai. The C-C bond cleavage inhibition and intermediates adsorption enhancement co-boost the selective electrooxidation of ethylene glycol on silver-palladium hollow nanocubes[J]. Chinese Journal of Catalysis, 2026, 86: 191-200.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65015-2

https://www.cjcatal.com/EN/Y2026/V86/I7/191

Figures/Tables 5

Fig. 1. TEM image (a), element mapping (b), EDX linear scanning at the shell region (c), HAADF-STEM image (d), and magnified HAADF-STEM image (e) of AgPd hNCs.

Fig. 2. XRD pattern (a), Ag 3d XPS spectrum (b), and Pd 3d XPS spectrum (c) of AgPd hNCs. (d) Normalized Pd K-edge XANES for Pd foil, AgPd hNCs and PdO. (e) FT-EXAFS spectrum of AgPd hNCs, Pd foil and PdO. WT-EXAFS spectra of Pd in Pd foil (f), AgPd hNCs (g), and PdO (h).

Fig. 3. (a) CV curves of AgPd hNCs, Ag NCs and Pd black in N2-saturated 1.0 mol L?1 KOH solution at 0.05 V s?1. (b) CV curves of AgPd hNCs and Pd black in N2-saturated 1.0 mol L?1 EG + 1.0 mol L?1 KOH solutions at 0.05 V s?1. (c) A partial enlargement of Fig. 3(b). (d) CV curves of samples with different Ag/Pd ratios in N2-saturated 1.0 mol L?1 EG + 1.0 mol L?1 KOH solutions at 0.05 V s?1. (e) Nyquist plots of AgPd hNCs and Pd black. (f) CO stripping curves of AgPd hNCs and Pd black at 0.05 V s?1. (g) Chronoamperometric curves of AgPd hNCs and Pd black in N2-saturated 1.0 mol L?1 EG + 1.0 mol L?1 KOH solutions at 0.94 V vs. RHE.

Fig. 4. (a) 1H NMR analysis of the electrolytes after EGOR on AgPd hNCs. (b) Faradaic efficiency of AgPd hNCs and Pd black at different potentials. (c) In-situ Raman spectra of EGOR at AgPd hNCs with potential changes. (d) In-situ FTIR spectra of EGOR at AgPd hNCs with potential changes.

Fig. 5. (a) Schematic diagram of the reaction process. (b) Gibbs free energy diagrams of EGOR on the Ag(001), Pd(111), and AgPd(001). (c) Density of states of Pd(111) and AgPd(001). (d) Charge density difference of AgPd(001) and Pd(111) induced by the adsorption of *CH2OH-CHO. Deep pink, green, brown, red, and light pink spheres represent Pd, Ag, C, O, and H atoms, respectively.

References

[1]	M. K. M. Lane, H. E. Rudel, J. A. Wilson, H. C. Erythropel, A. Backhaus, E. B. Gilcher, M. Ishii, C. F. Jean, F. Lin, T. D. Muellers, T. Wang, G. Torres, D. E. Taylor, P. T. Anastas, J. B. Zimmerman, Nat. Sustain., 2023, 6, 502-512.
[2]	C. Dai, J. Zhang, C. Huang, Z. Lei, Chem. Rev., 2017, 117, 6929-6983.
[3]	H. Fujisaki, T. Ishizuka, H. Kotani, Y. Shiota, K. Yoshizawa, T. Kojima, Nature, 2023, 616, 476-481.
[4]	A. Jalil, E. E. Happel, L. Cramer, A. Hunt, A. S. Hoffman, I. Waluyo, M. M. Montemore, P. Christopher, E. C. H. Sykes, Science, 2025, 387, 869-873.
[5]	L. Xiong, J. Tang, Adv. Energy Mater., 2021, 11, 2003216.
[6]	X. Li, T. Yang, J. Li, X. Li, P. Chen, Z. Lin, G. Liu, Nat. Chem., 2023, 15, 862-871.
[7]	Z.-H. Yuan, B. Sun, Q.-L. Hong, X. Ai, S.-B. Yin, F.-M. Li, J. Bai, Y. Chen, Carbon Energy, 2025, 7, e70020.
[8]	X.-L. Liu, W. Zhong, Y.-F. Jin, T.-J. Wang, X. Xiao, P. Chen, Y. Chen, X. Ai, Chin. J. Catal., 2025, 69, 241-248.
[9]	X. Zhu, Y. Ding, S. Li, Y. Jiang, Y. Chen, Sci. Bull., 2024, 69, 483-491.
[10]	S.-H. Shi, Y. Liang, N. Jiao, Chem. Rev., 2021, 121, 485-505.
[11]	Y. Lum, J. E. Huang, Z. Wang, M. Luo, D.-H. Nam, W. R. Leow, B. Chen, J. Wicks, Y. C. Li, Y. Wang, C.-T. Dinh, J. Li, T.-T. Zhuang, F. Li, T.-K. Sham, D. Sinton, E. H. Sargent, Nat. Catal., 2020, 3, 14-22.
[12]	L. Li, C. Tang, Y. Zheng, B. Xia, X. Zhou, H. Xu, S.-Z. Qiao, Adv. Energy Mater., 2020, 10, 2000789.
[13]	Y. Huang, L. Zou, Y.-B. Huang, R. Cao, Chin. J. Catal., 2025, 70, 207-229.
[14]	C. Xia, Nat. Catal., 2023, 6, 559-560.
[15]	L. Fan, Y. Zhao, L. Chen, J. Chen, J. Chen, H. Yang, Y. Xiao, T. Zhang, J. Chen, L. Wang, Nat. Catal., 2023, 6, 585-595.
[16]	Y. Lin, Y. Chen, H. Ren, Y. Sun, J. Chen, M. Wu, Z. Li, Adv. Funct. Mater., 2024, 34, 2404594.
[17]	H. Baniamerian, M. Høj, M. J. Beier, A. D. Jensen, Appl. Catal. B, 2023, 330, 122650.
[18]	P. F. South, A. P. Cavanagh, H. W. Liu, D. R. Ort, Science, 2019, 363, eaat9077.
[19]	J. Chen, J. Li, Z. Wei, Chin. J. Catal., 2025, 73, 79-98.
[20]	J. Chen, M. Jiang, F. Zhang, L. Wang, J. Yang, Adv. Mater., 2024, 36, 2401867.
[21]	K. Shi, D. Si, X. Teng, L. Chen, J. Shi, Nat. Commun., 2024, 15, 2899.
[22]	Z. Wang, J. Li, Q. Zhang, C. Wu, H. Meng, Y. Tang, A. Zou, Y. Zhang, R. Ma, X. Lv, Z. Yu, S. Xi, J. Xue, X. Wang, J. Wu, Angew. Chem. Int. Ed., 2024, 63, e202411517.
[23]	H. Lv, Y. Mao, H. Yao, H. Ma, C. Han, Y.-Y. Yang, Z.-A. Qiao, B. Liu, Angew. Chem. Int. Ed., 2024, 63, e202400281.
[24]	C. He, Y. Yan, Y. Fu, C. Ma, J. Xia, S. Han, H. Zhang, X. Ma, G. Lin, F. Feng, X. Meng, W. Cao, L. Zhu, Z. Li, Q. Lu, Adv. Mater., 2025, 37, 2418959.
[25]	X. Yu, J. Liu, J. Li, Z. Luo, Y. Zuo, C. Xing, J. Llorca, D. Nasiou, J. Arbiol, K. Pan, T. Kleinhanns, Y. Xie, A. Cabot, Nano Energy, 2020, 77, 105116.
[26]	X. Huang, O. Akdim, M. Douthwaite, K. Wang, L. Zhao, R. J. Lewis, S. Pattisson, I. T. Daniel, P. J. Miedziak, G. Shaw, D. J. Morgan, S. M. Althahban, T. E. Davies, Q. He, F. Wang, J. Fu, D. Bethell, S. McIntosh, C. J. Kiely, G. J. Hutchings, Nature, 2022, 603, 271-275.
[27]	G. Liu, W. Zhou, Y. Ji, B. Chen, G. Fu, Q. Yun, S. Chen, Y. Lin, P.-F. Yin, X. Cui, J. Liu, F. Meng, Q. Zhang, L. Song, L. Gu, H. Zhang, J. Am. Chem. Soc., 2021, 143, 11262-11270.
[28]	B.-Q. Miao, Z.-H. Yuan, X.-L. Liu, X. Ai, G.-T. Zhao, P. Chen, P.-J. Jin, Y. Chen, Chin. J. Chem., 2024, 42, 2633-2640.
[29]	E. A. Moges, C.-Y. Chang, W.-H. Huang, K. Lakshmanan, Y. A. Awoke, C.-W. Pao, M.-C. Tsai, W.-N. Su, B. J. Hwang, Adv. Funct. Mater., 2022, 32, 2206887.
[30]	Y. Qin, W. Zhang, F. Wang, J. Li, J. Ye, X. Sheng, C. Li, X. Liang, P. Liu, X. Wang, X. Zheng, Y. Ren, C. Xu, Z. Zhang, Angew. Chem. Int. Ed., 2022, 61, e202200899.
[31]	G.-R. Xu, Z. Dong, Y. Zhao, W. Zhang, Q. Sun, D. Ju, L. Wang, Small, 2024, 20, 2306341.
[32]	D. Ma, Y. Ying, K. Zhang, Y. Gao, L. Zhou, A. Song, Y. Zhu, K. Xie, T. Jin, H. Huang, Appl. Catal. B, 2022, 316, 121658.
[33]	Q. Hu, P. Li, M. Li, J. Wu, W. Fan, H. Zhang, X. Jiao, Q. Chen, Small, 2025, 21, 2503445.
[34]	H.-Q. Fu, J. Liu, N. M. Bedford, Y. Wang, J.-W. Sun, Y. Zou, M. Dong, J. Wright, H. Diao, P. Liu, H.-G. Yang, H. Zhao, Adv. Mater., 2022, 34, 2202854.
[35]	F. Qiao, Nano Res. Energy, 2025, 4, e9120132.
[36]	Q. Wang, H. Wei, P. Liu, Z. Su, X.-Q. Gong, Nano Res. Energy, 2024, 3, e9120112.
[37]	S.-N. Li, J. Yao, S. Pang, J.-P. Zhang, S. Li, Z. Liu, L. Han, W. Fan, K. Zhu, Y.-A. Zhu, Chin. J. Catal., 2025, 74, 82-96.
[38]	Y. Yang, J. Zhang, Z. Tan, J. Yang, S. Wang, M. Li, Z. Su, Angew. Chem. Int. Ed., 2024, 63, e202408873.
[39]	L. Huang, J. Zou, J.-Y. Ye, Z.-Y. Zhou, Z. Lin, X. Kang, P. K. Jain, S. Chen, Angew. Chem. Int. Ed., 2019, 58, 8794-8798.
[40]	A. J. Martín, S. Mitchell, C. Mondelli, S. Jaydev, J. Pérez-Ramírez, Nat. Catal., 2022, 5, 854-866.
[41]	J. Qi, N. Benipal, C. Liang, W. Li, Appl. Catal. B, 2016, 199, 494-503.
[42]	F. Gao, Y. Zhang, F. Ren, Y. Shiraishi, Y. Du, Adv. Funct. Mater., 2020, 30, 2000255.
[43]	J. Easa, C. Yan, W. F. Schneider, C. P. O’Brien, Chem. Eng. J., 2022, 430, 133080.
[44]	F. R. Negreiros, A. Halder, C. Yin, A. Singh, G. Barcaro, L. Sementa, E. C. Tyo, M. J. Pellin, S. Bartling, K.-H. Meiwes-Broer, S. Seifert, P. Sen, S. Nigam, C. Majumder, N. Fukui, H. Yasumatsu, S. Vajda, A. Fortunelli, Angew. Chem. Int. Ed., 2018, 57, 1209-1213.
[45]	C. C. Lima, M. V. F. Rodrigues, A. F. M. Neto, C. R. Zanata, C. T. G. V. M. T. Pires, L. S. Costa, J. Solla-Gullón, P. S. Fernández, Appl. Catal. B, 2020, 279, 119369.
[46]	M. L. Frisch, L. Wu, C. Atlan, Z. Ren, M. Han, R. Tucoulou, L. Liang, J. Lu, A. Guo, H. N. Nong, A. Arinchtein, M. Sprung, J. Villanova, M.-I. Richard, P. Strasser, Nat. Commun., 2023, 14, 7833.
[47]	Q. Li, S. Yang, R. Liu, Y. Huang, Y. Liang, C. Hu, M. Wang, Z. Liu, Y. Tai, J. Liu, Y. Li, Appl. Catal. B, 2023, 331, 122700.
[48]	Y. Wan, W. Wei, S. Ding, L. Wu, H. Qin, X. Yuan, Adv. Funct. Mater., 2025, 35, 2414554.
[49]	S. W. Chee, S.-F. Tan, Z. Baraissov, M. Bosman, U. Mirsaidov, Nat. Commun., 2017, 8, 1224.
[50]	J. Chen, S. Li, V. Kumar, P. S. Lee, Adv. Energy Mater., 2017, 7, 1700180.
[51]	C. Liu, X. Huang, J. Wang, H. Song, Y. Yang, Y. Liu, J. Li, L. Wang, C. Yu, Adv. Funct. Mater., 2018, 28, 1705253.
[52]	J. Wang, Q. Ma, Y. Wang, Z. Li, Z. Li, Q. Yuan, Chem. Soc. Rev., 2018, 47, 8766-8803.
[53]	J. A. Zamora Zeledón, M. B. Stevens, G. T. Kasun Kalhara Gunasooriya, A. Gallo, A. T. Landers, M. E. Kreider, C. Hahn, J. K. Nørskov, T. F. Jaramillo, Nat. Commun., 2021, 12, 620.
[54]	D. A. Slanac, W. G. Hardin, K. P. Johnston, K. J. Stevenson, J. Am. Chem. Soc., 2012, 134, 9812-9819.
[55]	Y. Ma, J. Bansmann, T. Diemant, R. J. Behm, Surf. Sci., 2009, 603, 1046-1054.
[56]	H. Yang, B. Yan, Y. Xue, T. Guo, Z. Wang, G. Teobaldi, P. Hu, L.-M. Liu, L. Guo, Sci. Adv., 2025, 11, eadx8081.
[57]	W. Zhang, X. Hao, X. Liu, M. Chu, S. Li, X. Wang, F. Jiang, L. Wang, Q. Zhang, J. Chen, D. Wang, M. Cao, Angew. Chem. Int. Ed., 2025, 64, e202500814.
[58]	C. Hartwig, K. Schweinar, T. E. Jones, S. Beeg, F.-P. Schmidt, R. Schlögl, M. Greiner, J. Chem. Phys., 2021, 154, 184703.
[59]	T.-J. Wang, L.-B. Sun, X. Ai, P. Chen, Y. Chen, X. Wang, Adv. Mater., 2024, 36, 2403664.
[60]	M. Li, Z. Zhao, W. Zhang, M. Luo, L. Tao, Y. Sun, Z. Xia, Y. Chao, K. Yin, Q. Zhang, L. Gu, W. Yang, Y. Yu, G. Lu, S. Guo, Adv. Mater., 2021, 33, 2103762.
[61]	J.-J. Zhao, H.-R. Zhu, C.-J. Huang, M.-H. Yin, G.-R. Li, J. Mater. Chem. A, 2025, 13, 3236-3272.