Ligand-Wise Stripping Dictates Metal Ensemble Catalysts for Selective Oxidation of Biomass-Derived 5-HydroxymethylfurfuralOA
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-N_(2)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-N_(2)/Co_(4)dual-site catalyst achieves 98.76%FDCA yield at 55℃,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.
Junkai Li;Guanhua Wang;Yunxiang Wu;Chuqiao Song;Tairan Pang;Zechao Zhuang;Jiarui Yang;Wenjie Sui;Lili Lin;Dingsheng Wang;Ligang Wang;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 ChinaState 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 ChinaState 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 ChinaInstitute 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 ChinaState 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 ChinaDepartment of Chemistry,Tsinghua University,Beijing 100084,People’s Republic of ChinaDepartment of Chemistry,Tsinghua University,Beijing 100084,People’s Republic of ChinaState 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 ChinaInstitute 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 ChinaDepartment of Chemistry,Tsinghua University,Beijing 100084,People’s Republic of ChinaInstitute of Molecular Plus,Tianjin University,Tianjin 300072,People’s Republic of ChinaState 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
化学化工
Atom cluster catalystsSingle atomCluster synergistic catalysisCascade oxidation
《Nano-Micro Letters》 2026 (9)
P.77-92,16
supported by the National Natural Science Foundation of China(22578333)the Natural Science Foundation of Tianjin City(24JCZDJC00780)。
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