Engineering a localized electrostatic environment to enhance hydroxyl activating for electrocatalytic biomass conversion

doi:10.1016/S1872-2067(23)64516-4

Abstract

Abstract:

The 5-hydroxymethylfurfural electrocatalytic oxidation reaction (HMFOR) is a sustainable and efficient route for converting biomass platform molecules into high-value chemicals. The HMFOR process involves the simultaneous oxidation of hydroxyl and aldehyde groups. Optimizing the reaction pathways by modulating the adsorption behavior of 5-Hydroxymethylfurfural molecules toward a higher conversion rate is vital for achieving an efficient HMFOR. In this study, the HMFOR electrocatalytic performance of NiO was enhanced by regulating the surface microenvironment through the decoration of NiO nanosheets with polypyrrole (PPy). Operando Fourier transform infrared spectroscopy, density functional theory calculation, and electrochemical behavior characterizations demonstrated that electropositive PPy can optimize the adsorption behavior of electronegative hydroxyl groups and modulate the reaction pathway toward the formation of 2,5-diformylfuran intermediates. By modulating the local microenvironment, the designed NiO-PPy catalyst showed excellent HMFOR performance with a threefold increase in current density. This study emphasizes the significance of the surface microenvironment in modulating reaction pathways to achieve selective biomass electrocatalytic conversion.

Key words: Electrocatalyst, Surface micro-environment, Biomass upgrading, Polymer modification, Electrocatalytic oxidation

Yuxuan Lu, Liu Yang, Yimin Jiang, Zhenran Yuan, Shuangyin Wang, Yuqin Zou. Engineering a localized electrostatic environment to enhance hydroxyl activating for electrocatalytic biomass conversion[J]. Chinese Journal of Catalysis, 2023, 53: 153-160.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64516-4

https://www.cjcatal.com/EN/Y2023/V53/I10/153

Figures/Tables 4

Fig. 1. (a) XRD patterns of NiO and NiO-PPy. (b) FT-IR spectra of NiO and NiO-PPy. HR-TEM images of NiO (c) and NiO-PPy (d). (e) XPS survey spectra of NiO-PPy. (f) N 1s in the NiO-PPy.

Fig. 2. (a) LSV curves of HMFOR on PPy, NiO, and NiO-PPy at a scan rate of 5 mV s?1. (b) Tafel slope of NiO and NiO-PPy. (c) Relative content of HMF during the electrolysis on NiO and NiO-PPy at the potential of 1.45 VRHE. (d) HMF conversion and FDCA yield of NiO-PPy under six successive electrolysis cycles at the potential of 1.45 VRHE and the electrolysis time of 1.5 h. (e) FT-IR spectra of NiO-PPy before and after electrolysis. (f) XPS spectra of N 1s in NiO-PPy before and after electrolysis.

Fig. 3. (a) OCP measurement of NiO and NiO-PPy. (b) EQCM curves of NiO and NiO-PPy. (c) Detailed HMF oxidation reaction pathways. (d) Concentration of HMFCA and DFF on NiO and NiO-PPy during HMFOR. (e) Concentration of intermediates on NiO-PPy during HMFOR. Operando FT-IR spectra of NiO (f) and NiO-PPy (g).

Fig. 4. (a) LSV curves of NiO and NiO-PPy in 1 mol L?1 KOH or with 50 mmol L?1 organic molecule. (b) Comparison of HMFOR, FAOR, and FFOR performance between NiO-PPy and NiO at the potential of 1.45 VRHE. (c) Adsorption model of HMF molecule on NiO and NiO-PPy. (d) Comparison of the adsorption energy of HMF molecule on NiO and NiO-PPy. (e) Scheme for the modulation of the surface micro-environment by decorating PPy on NiO to achieve HMFOR process.

References

[1]	A. Grimaud, O. Diaz-Morales, B. Han, W. T. Hong, Y. L. Lee, L. Giordano, K. A. Stoerzinger, M. T. M. Koper, Y. Shao-Horn, Nat. Chem., 2017, 9, 457-465.
[2]	H. Zhao, D. Lu, J. Wang, W. Tu, D. Wu, S. W. Koh, P. Gao, Z. J. Xu, S. Deng, Y. Zhou, B. You, H. Li, Nat. Commun., 2021, 12, 2008.
[3]	J. J. Bozell, G. R. Petersen. Green Chem., 2010, 12, 539-554.
[4]	S. Rajendran, R. Raghunathan, I. Hevus, R. Krishnan, A. Ugrinov, M. P. Sibi, D. C. Webster, J. Sivaguru, Angew. Chem. Int. Ed., 2015, 54, 1159-1163.
[5]	C. Chen, L. Wang, B. Zhu, Z. Zhou, S. El-Hout, J. Yang, J. Zhang, J. Energy Chem., 2021, 54, 528-554.
[6]	B. You, N. Jiang, X. Liu, Y. Sun, Angew. Chem. Int. Ed., 2016, 55, 9913-9917.
[7]	C. Xu, E. Paone, D. Rodriguez-Padron, R. Luque, F. Mauriello, Chem. Soc. Rev., 2020, 49, 4273-4306
[8]	Y. Lu, T. Liu, Y.-C. Huang, L. Zhou, Y. Li, W. Chen, L. Yang, B. Zhou, Y. Wu, Z. Kong, Z. Huang, Y. Li, C.-L. Dong, S. Wang, Y. Zou, ACS Catal., 2022, 12, 4242-4251.
[9]	Z. Li, Y. Yan, S. M. Xu, H. Zhou, M. Xu, L. Ma, M. Shao, X. Kong, B. Wang, L. Zheng, H. Duan, Nat. Commun., 2022, 13, 147
[10]	X. Deng, G. Y. Xu, Y. J. Zhang, L. Wang, J. Zhang, J. F. Li, X. Z. Fu, J. L. Luo, Angew. Chem. Int. Ed., 2021, 60, 20535-20542.
[11]	R. Ge, Y. Wang, Z. Li, M. Xu, S. M. Xu, H. Zhou, K. Ji, F. Chen, J. Zhou, H. Duan, Angew. Chem. Int. Ed., 2022, 61, e202200211.
[12]	B. Zhou, C.-L. Dong, Y.-C. Huang, N. Zhang, Y. Wu, Y. Lu, X. Yue, Z. Xiao, Y. Zou, S. Wang, J. Energy Chem., 2021, 61, 179-185.
[13]	W. Kohn, L. J. Sham. Phys. Rev., 1965, 140, A1133-A1138
[14]	G. Kresse, J. Hafner, Phys. Rev. B, 1993, 48, 13115-13118
[15]	S. L. Dudarev, G. A. Botton, S. Y. Savrasov, C. J. Humphreys, A. P. Sutton, Phys. Rev. B, 1998, 57, 1505-1509.
[16]	J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
[17]	V. V. Anisimov, J. Zaanen, O. K. Andersen, Phys. Rev. B, 1991, 44, 943-954.
[18]	S. Grimme, J. Comput. Chem., 2006, 27, 1787-1799
[19]	D. Zhao, M. Dai, Y. Zhao, H. Liu, Y. Liu, X. Wu, Nano Energy, 2020, 72, 104715.
[20]	D. Zhao, H. Liu, X. Wu, Nano Energy, 2019, 57, 363-370.
[21]	S. U. Muhamad, N. H. Idris, H. M. Yusoff, M. M. Din, S. Majid, Electrochim. Acta, 2017, 249, 9-15.
[22]	C. Yang, L. Zhang, N. Hu, Z. Yang, H. Wei, Y. Zhang. J. Power Sources, 2016, 302, 39-45.
[23]	Y. Chen, L. Shen, C. Wang, S. Feng, N. Zhang, S. Xiang, T. Feng, M. Yang, K. Zhang, B. Yang, Appl. Catal. B, 2020, 274, 119112.
[24]	H. Xu, D. Cheng, D. Cao, X. C. Zeng, Nat. Catal., 2018, 1, 339-348.
[25]	Y. Lu, C.-L. Dong, Y.-C. Huang, Y. Zou, Y. Liu, Y. Li, N. Zhang, W. Chen, L. Zhou, H. Lin, S. Wang, Sci. China Chem., 2020, 63, 980-986.
[26]	H. Yang, B. Liu, J. Bright, S. Kasani, J. Yang, X. Zhang, N. Wu, ACS Appl. Energy Mater., 2020, 3, 4007-4013.
[27]	H. Y. Wang, S. F. Hung, H. Y. Chen, T. S. Chan, H. M. Chen, B. Liu, J. Am. Chem. Soc., 2016, 138, 36-39,
[28]	Y. Wu, C. Liu, C. Wang, Y. Yu, Y. Shi, B. Zhang, Nat. Commun., 2021, 12, 3881
[29]	Y. Lu, T. Liu, C. L. Dong, Y. C. Huang, Y. Li, J. Chen, Y. Zou, S. Wang, Adv. Mater., 2021, 33, 2007056.
[30]	Z. Li, X. Li, H. Zhou, Y. Xu, S. M. Xu, Y. Ren, Y. Yan, J. Yang, K. Ji, L. Li, M. Xu, M. Shao, X. Kong, X. Sun, H. Duan, Nat. Commun., 2022, 13, 5009.
[31]	A. R. Poerwoprajitno, L. Gloag, J. Watt, S. Cychy, S. Cheong, P. V. Kumar, T. M. Benedetti, C. Deng, K. H. Wu, C. E. Marjo, D. L. Huber, M. Muhler, J. J. Gooding, W. Schuhmann, D. W. Wang, R. D. Tilley, Angew. Chem. Int. Ed., 2020, 59, 15487-15491.
[32]	N. Heidary, D. Chartrand, A. Guiet, N. Kornienko, Chem. Sci., 2021, 12, 7324-7333.
[33]	S. Barwe, J. Weidner, S. Cychy, D. M. Morales, S. Dieckhofer, D. Hiltrop, J. Masa, M. Muhler, W. Schuhmann, Angew. Chem. Int. Ed., 2018, 57, 11460-11464
[34]	H. Jiang, J. X. Gu, X. S. Zheng, M. Liu, X. Q. Qiu, L. B. Wang, W. Z. Li, Z. F. Chen, X. B. Ji, J. Li, Energy Environ. Sci., 2019, 12, 322-333