Rectifying lattice strain for selective photoelectrocatalytic conversion of lignin to aromatic acids

IF 11.2 1区 材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY
Wenliu Li, Jinshu Huang, Yuhe Liao, Bing Song, Hu Li
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Abstract

The *OH-mediated oxidative C(O)‒C bond breaking is an effective approach for biomass valorization but is often hampered by inefficient/competitive adsorption of the substrate and active species. Herein, a nickel doping-enabled strain engineering strategy is presented to modulate the binding ability of interfacial sites to better reduce the kinetic barriers of the reaction process. The Ni-doped CdS photoanode with an optimal strain degree of 4.85% could realize the photoelectrochemical conversion of bio-based acetophenone to benzoic acid in an ultrahigh yield of 97.6%, outperforming the state-of-the-art catalytic systems. Mechanistic investigations corroborate that the doping of Ni species into CdS nanosheets renders the electron transfer toward Cd sites and induces lattice distortion, which can facilitate the formation of *OH (on Ni with compressible strain) and adsorption of acetophenone (on Cd with tensile strain), significantly alleviating intrinsic competitive adsorption in single sites. Moreover, the strain effect enables the moving down of d orbitals of Ni sites toward the Fermi level to promote the desorption of generated *OH for subsequent nucleophilic attack of acetophenone preactivated by Cd sites, contributing to the enhanced C(O)‒C bond cleavage to afford benzoic acid. The developed photoanode was applicable to the oxidative C–C bond cleavage of various aromatic alcohols and carbonyls containing C(O)–C motifs in lignin derivatives to benzoic acids (85%–99% yields). The two-site lattice strain engineering offers a viable route to activate both substrate and catalytic species for enhanced biomass conversion and organic transformations.

Abstract Image

选择性光电催化木质素转化为芳香酸的精馏晶格应变
* oh介导的氧化C(O) -C键断裂是生物质增值的有效途径,但往往受到底物和活性物质的低效/竞争性吸附的阻碍。本文提出了一种掺杂镍的应变工程策略来调节界面位点的结合能力,以更好地降低反应过程的动力学障碍。最佳应变度为4.85%的ni掺杂CdS光阳极可实现生物基苯乙酮转化为苯甲酸的超高产率(97.6%),优于现有的催化体系。机制研究证实,Ni掺杂到CdS纳米片中,使电子向Cd位点转移并引起晶格畸变,从而促进*OH(在Ni上具有可压缩应变)的形成和苯乙酮(在Cd上具有拉伸应变)的吸附,显著减轻了单位点的内在竞争性吸附。此外,应变效应使Ni位点的d轨道向费米能级下移,促进生成的*OH的解吸,以备Cd位点预激活的苯乙酮随后的亲核攻击,从而促进C(O) -C键的增强裂解,从而产生苯甲酸。所制备的光阳极适用于木质素衍生物中含C(O) -C基的各种芳香醇和羰基的C -C键氧化裂解(产率85% ~ 99%)。双向晶格应变工程为激活底物和催化物质以增强生物质转化和有机转化提供了一条可行的途径。
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来源期刊
Journal of Materials Science & Technology
Journal of Materials Science & Technology 工程技术-材料科学:综合
CiteScore
20.00
自引率
11.00%
发文量
995
审稿时长
13 days
期刊介绍: Journal of Materials Science & Technology strives to promote global collaboration in the field of materials science and technology. It primarily publishes original research papers, invited review articles, letters, research notes, and summaries of scientific achievements. The journal covers a wide range of materials science and technology topics, including metallic materials, inorganic nonmetallic materials, and composite materials.
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