Cooperative Rh-O5/Ni(Fe) Site for Efficient Biomass Upgrading Coupled with H2 Production

Lingyou Zeng; Yanju Chen; Mingzi Sun; Qizheng Huang; Kaian Sun; Jingyuan Ma; Jiong Li; Hao Tan; Menggang Li; Yuan Pan; Yunqi Liu; Mingchuan Luo; Bolong Huang; Shaojun Guo

doi:10.1021/jacs.3c02570

Cooperative Rh-O₅/Ni(Fe) Site for Efficient Biomass Upgrading Coupled with H₂ Production

Lingyou Zeng, Yanju Chen, Mingzi Sun, Qizheng Huang, Kaian Sun, Jingyuan Ma, Jiong Li, Hao Tan, Menggang Li, Yuan Pan, Yunqi Liu, Mingchuan Luo, Bolong Huang^*, Shaojun Guo^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

182 Citations (Scopus)

Abstract

Designing efficient and durable bifunctional catalysts for 5-hydroxymethylfurfural (HMF) oxidation reaction (HMFOR) and hydrogen evolution reaction (HER) is desirable for the co-production of biomass-upgraded chemicals and sustainable hydrogen, which is limited by the competitive adsorption of hydroxyl species (OH_ads) and HMF molecules. Here, we report a class of Rh-O₅/Ni(Fe) atomic site on nanoporous mesh-type layered double hydroxides with atomic-scale cooperative adsorption centers for highly active and stable alkaline HMFOR and HER catalysis. A low cell voltage of 1.48 V is required to achieve 100 mA cm^-2 in an integrated electrolysis system along with excellent stability (>100 h). Operando infrared and X-ray absorption spectroscopic probes unveil that HMF molecules are selectively adsorbed and activated over the single-atom Rh sites and oxidized by in situ-formed electrophilic OH_ads species on neighboring Ni sites. Theoretical studies further demonstrate that the strong d-d orbital coupling interactions between atomic-level Rh and surrounding Ni atoms in the special Rh-O₅/Ni(Fe) structure can greatly facilitate surface electronic exchange-and-transfer capabilities with the adsorbates (OH_ads and HMF molecules) and intermediates for efficient HMFOR and HER. We also reveal that the Fe sites in Rh-O₅/Ni(Fe) structure can promote the electrocatalytic stability of the catalyst. Our findings provide new insights into catalyst design for complex reactions involving competitive adsorptions of multiple intermediates. © 2023 American Chemical Society.

Original language	English
Pages (from-to)	17577-17587
Journal	Journal of the American Chemical Society
Volume	145
Issue number	32
Online published	30 May 2023
DOIs	https://doi.org/10.1021/jacs.3c02570
Publication status	Published - 16 Aug 2023
Externally published	Yes

Funding

This work was supported by the National Natural Science Foundation of China (52002005, 52025133), China National Petroleum Corporation-Peking University Strategic Cooperation Project of Fundamental Research, CNPC Innovation Found (Grant No. 2021DQ02-1002), the New Cornerstone Science Foundation through the XPLORER PRIZE, the Fund of the State Key Laboratory of Solidification Processing in NWPU (SKLSP202004), the National Key R&D Program of China (2021YFA1501101), the National Natural Science Foundation of China/Research Grant Council of Hong Kong Joint Research Scheme (N_PolyU502/21), the funding for Projects of Strategic Importance of The Hong Kong Polytechnic University (Project Code: 1-ZE2V), the National Natural Science Foundation of China/Research Grants Council (RGC) of Hong Kong Collaborative Research Scheme (CRS_PolyU504_22), the Shenzhen Fundamental Research Scheme-General Program (JCYJ20220531090807017), the Natural Science Foundation of Guangdong Province (2023A1515012219), and Departmental General Research Fund (Project Code: ZVUL) from The Hong Kong Polytechnic University. The authors thank the photoemission photoendstations BL14W1 and BL11B in the Shanghai Synchrotron Radiation Facility (SSRF), BL1W1B in the Beijing Synchrotron Radiation Facility (BSRF) for the help with characterizations, and the support from Research Centre for Carbon-Strategic Catalysis of The Hong Kon Polytechnic University.

RGC Funding Information

RGC-funded

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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Cite this

@article{a82f38fa0ddb4dd7a15e6f68d1a7efae,

title = "Cooperative Rh-O5/Ni(Fe) Site for Efficient Biomass Upgrading Coupled with H2 Production",

abstract = "Designing efficient and durable bifunctional catalysts for 5-hydroxymethylfurfural (HMF) oxidation reaction (HMFOR) and hydrogen evolution reaction (HER) is desirable for the co-production of biomass-upgraded chemicals and sustainable hydrogen, which is limited by the competitive adsorption of hydroxyl species (OHads) and HMF molecules. Here, we report a class of Rh-O5/Ni(Fe) atomic site on nanoporous mesh-type layered double hydroxides with atomic-scale cooperative adsorption centers for highly active and stable alkaline HMFOR and HER catalysis. A low cell voltage of 1.48 V is required to achieve 100 mA cm-2 in an integrated electrolysis system along with excellent stability (>100 h). Operando infrared and X-ray absorption spectroscopic probes unveil that HMF molecules are selectively adsorbed and activated over the single-atom Rh sites and oxidized by in situ-formed electrophilic OHads species on neighboring Ni sites. Theoretical studies further demonstrate that the strong d-d orbital coupling interactions between atomic-level Rh and surrounding Ni atoms in the special Rh-O5/Ni(Fe) structure can greatly facilitate surface electronic exchange-and-transfer capabilities with the adsorbates (OHads and HMF molecules) and intermediates for efficient HMFOR and HER. We also reveal that the Fe sites in Rh-O5/Ni(Fe) structure can promote the electrocatalytic stability of the catalyst. Our findings provide new insights into catalyst design for complex reactions involving competitive adsorptions of multiple intermediates. {\textcopyright} 2023 American Chemical Society.",

author = "Lingyou Zeng and Yanju Chen and Mingzi Sun and Qizheng Huang and Kaian Sun and Jingyuan Ma and Jiong Li and Hao Tan and Menggang Li and Yuan Pan and Yunqi Liu and Mingchuan Luo and Bolong Huang and Shaojun Guo",

year = "2023",

month = aug,

day = "16",

doi = "10.1021/jacs.3c02570",

language = "English",

volume = "145",

pages = "17577--17587",

journal = "Journal of the American Chemical Society",

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T1 - Cooperative Rh-O5/Ni(Fe) Site for Efficient Biomass Upgrading Coupled with H2 Production

AU - Zeng, Lingyou

AU - Chen, Yanju

AU - Sun, Mingzi

AU - Huang, Qizheng

AU - Sun, Kaian

AU - Ma, Jingyuan

AU - Li, Jiong

AU - Tan, Hao

AU - Li, Menggang

AU - Pan, Yuan

AU - Liu, Yunqi

AU - Luo, Mingchuan

AU - Huang, Bolong

AU - Guo, Shaojun

PY - 2023/8/16

Y1 - 2023/8/16

N2 - Designing efficient and durable bifunctional catalysts for 5-hydroxymethylfurfural (HMF) oxidation reaction (HMFOR) and hydrogen evolution reaction (HER) is desirable for the co-production of biomass-upgraded chemicals and sustainable hydrogen, which is limited by the competitive adsorption of hydroxyl species (OHads) and HMF molecules. Here, we report a class of Rh-O5/Ni(Fe) atomic site on nanoporous mesh-type layered double hydroxides with atomic-scale cooperative adsorption centers for highly active and stable alkaline HMFOR and HER catalysis. A low cell voltage of 1.48 V is required to achieve 100 mA cm-2 in an integrated electrolysis system along with excellent stability (>100 h). Operando infrared and X-ray absorption spectroscopic probes unveil that HMF molecules are selectively adsorbed and activated over the single-atom Rh sites and oxidized by in situ-formed electrophilic OHads species on neighboring Ni sites. Theoretical studies further demonstrate that the strong d-d orbital coupling interactions between atomic-level Rh and surrounding Ni atoms in the special Rh-O5/Ni(Fe) structure can greatly facilitate surface electronic exchange-and-transfer capabilities with the adsorbates (OHads and HMF molecules) and intermediates for efficient HMFOR and HER. We also reveal that the Fe sites in Rh-O5/Ni(Fe) structure can promote the electrocatalytic stability of the catalyst. Our findings provide new insights into catalyst design for complex reactions involving competitive adsorptions of multiple intermediates. © 2023 American Chemical Society.

AB - Designing efficient and durable bifunctional catalysts for 5-hydroxymethylfurfural (HMF) oxidation reaction (HMFOR) and hydrogen evolution reaction (HER) is desirable for the co-production of biomass-upgraded chemicals and sustainable hydrogen, which is limited by the competitive adsorption of hydroxyl species (OHads) and HMF molecules. Here, we report a class of Rh-O5/Ni(Fe) atomic site on nanoporous mesh-type layered double hydroxides with atomic-scale cooperative adsorption centers for highly active and stable alkaline HMFOR and HER catalysis. A low cell voltage of 1.48 V is required to achieve 100 mA cm-2 in an integrated electrolysis system along with excellent stability (>100 h). Operando infrared and X-ray absorption spectroscopic probes unveil that HMF molecules are selectively adsorbed and activated over the single-atom Rh sites and oxidized by in situ-formed electrophilic OHads species on neighboring Ni sites. Theoretical studies further demonstrate that the strong d-d orbital coupling interactions between atomic-level Rh and surrounding Ni atoms in the special Rh-O5/Ni(Fe) structure can greatly facilitate surface electronic exchange-and-transfer capabilities with the adsorbates (OHads and HMF molecules) and intermediates for efficient HMFOR and HER. We also reveal that the Fe sites in Rh-O5/Ni(Fe) structure can promote the electrocatalytic stability of the catalyst. Our findings provide new insights into catalyst design for complex reactions involving competitive adsorptions of multiple intermediates. © 2023 American Chemical Society.

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DO - 10.1021/jacs.3c02570

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