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Vol. 18 (2026)

Ligand-Wise Stripping Dictates Metal Ensemble Catalysts for Selective Oxidation of Biomass-Derived 5-Hydroxymethylfurfural

https://doi.org/10.1007/s40820-026-02118-7
Junkai Li
State Key Laboratory of Bio‑based Fiber Materials, Tianjin Key Laboratory of Pulp and Paper, College of Light Industry Science and Technology, Tianjin University of Science and Technology, Tianjin 300457, People’s Republic of China
Guanhua Wang
State Key Laboratory of Bio‑based Fiber Materials, Tianjin Key Laboratory of Pulp and Paper, College of Light Industry Science and Technology, Tianjin University of Science and Technology, Tianjin 300457, People’s Republic of China
Yunxiang Wu
State Key Laboratory of Bio‑based Fiber Materials, Tianjin Key Laboratory of Pulp and Paper, College of Light Industry Science and Technology, Tianjin University of Science and Technology, Tianjin 300457, People’s Republic of China
Chuqiao Song
Institute of Industrial Catalysis, State Key Laboratory of Green Chemistry Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, People’s Republic of China
Tairan Pang
State Key Laboratory of Bio‑based Fiber Materials, Tianjin Key Laboratory of Pulp and Paper, College of Light Industry Science and Technology, Tianjin University of Science and Technology, Tianjin 300457, People’s Republic of China
Zechao Zhuang
Department of Chemistry, Tsinghua University, Beijing 100084, People’s Republic of China
Jiarui Yang
Department of Chemistry, Tsinghua University, Beijing 100084, People’s Republic of China
Wenjie Sui
State Key Laboratory of Food Nutrition and Safety, College of Food Science and Engineering, Tianjin University of Science and Technology, Tianjin 300457, People’s Republic of China
Lili Lin
Institute of Industrial Catalysis, State Key Laboratory of Green Chemistry Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, People’s Republic of China
Dingsheng Wang
Department of Chemistry, Tsinghua University, Beijing 100084, People’s Republic of China
Ligang Wang
Institute of Molecular Plus, Tianjin University, Tianjin 300072, People’s Republic of China
Chuanling Si
State Key Laboratory of Bio‑based Fiber Materials, Tianjin Key Laboratory of Pulp and Paper, College of Light Industry Science and Technology, Tianjin University of Science and Technology, Tianjin 300457, People’s Republic of China

Corresponding Author: Chuanling Si

sichli@tust.edu.cn

Nano-Micro Letters, Vol. 18 (2026), Article Number: 299

Abstract

Single-atom catalysts (SACs), with their well-defined active sites, demonstrate remarkable selectivity in biomass platform chemical conversions. However, the feature of single active site fails to synergistically regulate the divergent oxidation pathways of multiple functional groups, thereby restricting multi-step reaction efficiency. Herein, a “stepwise N-stripping” strategy is developed via lignin-derived N-doped carbon matrices, which achieves controlled evolution from isolated Co-N4 single site to multi-scale atomic/cluster Co synergistic sites by precisely modulating the pyrolysis pathways of lignin-Co precursors. Theoretical and experimental evidence elucidates a synergy-enhanced tandem dual-site catalytic mechanism that single Co atoms with Co-N2 configuration selectively activate aldehyde groups to drive sequential carboxylation (5-hydroxymethylfurfural (HMF) to 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) and 5-formyl-2-furoic acid (FFCA) to 2,5-furandicarboxylic acid (FDCA)), while Co clusters enhance oxygen activation for accelerated hydroxymethyl oxidation (HMFCA to FFCA). As expected, the optimized Co-N2/Co4 dual-site catalyst achieves 98.76% FDCA yield at 55 °C, surpassing most reported supported metal catalysts, alongside robust cycling stability (6 cycles with > 97% FDCA yield). This work establishes a biomass-tailored paradigm for constructing atomic/cluster hybrid catalysts and unravels the dynamic cooperation mechanism between distinct active sites in multi-step oxidation, advancing the rational design of efficient systems for biomass valorization.


Highlights:
1 Lignin-tailored Co-N2/Co4 catalyst with tunable active sites were constructed by the “stepwise N-stripping” strategy.
2 Co-N2 and Co4 sites collaboratively drove cascade oxidation of –CH2OH and –CHO groups.
3 A record 2,5-furandicarboxylic acid yield of 98.76% was achieved under mild conditions over the dual-site catalyst.

Keywords

Atom cluster catalysts Single atom Cluster synergistic catalysis Cascade oxidation
Li, Junkai, Guanhua Wang, Yunxiang Wu, Chuqiao Song, Tairan Pang, Zechao Zhuang, Jiarui Yang, Wenjie Sui, Lili Lin, Dingsheng Wang, Ligang Wang, and Chuanling Si. 2026. “Ligand-Wise Stripping Dictates Metal Ensemble Catalysts for Selective Oxidation of Biomass-Derived 5-Hydroxymethylfurfural”. Nano-Micro Letters 18 (March):299. https://doi.org/10.1007/s40820-026-02118-7.
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