Atomic Ruthenium‐Promoted Cadmium Sulfide for Photocatalytic Production of Amino Acids from Biomass Derivatives

• Published in: Angewandte Chemie International Edition 2024-07, Vol.63 (27), p.e202320014-n/a
• Main Authors: Li, Wulin, Zheng, Xiuhui, Xu, Bei‐Bei, Yang, Yue, Zhang, Yifei, Cai, Lingchao, Wang, Zhu‐Jun, Yao, Ye‐Feng, Nan, Bing, Li, Lina, Wang, Xue‐Lu, Feng, Xiang, Antonietti, Markus, Chen, Zupeng
• Format: Article
• Language: English
• Subjects: Alanine; Amination; Amino acids; Biomass; biomass derivatives; Cadmium; Cadmium sulfide; Density functional theory; Hydrogen bonds; Hydroxy acids; Irradiation; Lactic acid; Light irradiation; Nanoparticles; NMR; Nuclear magnetic resonance; photocatalysis; Ruthenium; single-atom catalysis; Sulfides; Sustainable production
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202320014

Amino acids are the building blocks of proteins and are widely used as important ingredients for other nitrogen‐containing molecules. Here, we report the sustainable production of amino acids from biomass‐derived hydroxy acids with high activity under visible‐light irradiation and mild conditions, using atomic ruthenium‐promoted cadmium sulfide (Ru1/CdS). On a metal basis, the optimized Ru1/CdS exhibits a maximal alanine formation rate of 26.0 molAla ⋅ gRu−1 ⋅ h−1, which is 1.7 times and more than two orders of magnitude higher than that of its nanoparticle counterpart and the conventional thermocatalytic process, respectively. Integrated spectroscopic analysis and density functional theory calculations attribute the high performance of Ru1/CdS to the facilitated charge separation and O−H bond dissociation of the α‐hydroxy group, here of lactic acid. The operando nuclear magnetic resonance further infers a unique “double activation” mechanism of both the CH−OH and CH3−CH−OH structures in lactic acid, which significantly accelerates its photocatalytic amination toward alanine. Here we report ruthenium single‐atom catalysts loaded on ultrathin CdS nanosheets (Ru1/CdS), which efficiently catalyze biomass‐derived α‐hydroxy acids to produce amino acids under visible light irradiation. The optimal system predominates the conventional thermocatalytic and photocatalytic systems in terms of conversion, selectivity, yield, and amino acid formation rates.