北京大学郭少军团队报道了Rh-O₅/Ni（Fe）协同位点用于生物质高效升级与H₂生产。相关研究成果于2023年5月30日发表在《美国化学会杂志》。

为5-羟甲基糠醛（HMF）氧化反应（HMFOR）和析氢反应（HER）设计高效耐用的双功能催化剂，是生物质升级化学品和可持续氢气的共同生产所需要的，而可持续氢气受到羟基物种（OHads）和HMF分子竞争吸附的限制。

该文中，研究人员报道了一类在纳米多孔网状层状双氢氧化物上，具有原子级协同吸附中心，用于高活性和稳定的碱性HMFOR和HER催化的Rh–O₅/Ni（Fe）原子位。在集成电解系统中，需要1.48 V的低电池电压才能实现100 mA cm^–2，同时具有优异的稳定性（>100 h）。操作红外和X射线吸收光谱探针揭示了HMF分子在单原子Rh位点上被选择性吸附和活化，并被相邻Ni位点上原位形成的亲电OHads物种氧化。

理论研究进一步表明，在特殊的Rh–O₅/Ni（Fe）结构中，原子级Rh和周围Ni原子之间的强d–d轨道耦合相互作用，可以极大地促进与吸附质（OHads和HMF分子）和中间体的表面电子交换和转移能力，从而实现高效的HMFOR和HER。研究人员还揭示了Rh–O₅/Ni（Fe）结构中的Fe位点可以提高催化剂的电催化稳定性。

该发现为涉及多种中间体竞争吸附的复杂反应的催化剂设计提供了新的见解。

附：英文原文

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

Author: 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

Issue&Volume: May 30, 2023

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.

DOI: 10.1021/jacs.3c02570

Source: https://pubs.acs.org/doi/10.1021/jacs.3c02570