Cai Wei, Liu Jincheng, Luo Yijun, Liao Zewei, Li Bingjie, Xiang Xiaoyan, Fang Yanxiong
Guangdong University of Technology, School of Light Industry & Chemical Engineering, Guangzhou Key Lab Clean Transport Energy Chemistry, Guangzhou 510006, China; School of Advanced Manufacturing, Guangdong University of Technology, Jieyang Center of Chemistry and Chemical Engineering Guangdong Laboratory, Jieyang 515200, China.
Guangdong University of Technology, School of Light Industry & Chemical Engineering, Guangzhou Key Lab Clean Transport Energy Chemistry, Guangzhou 510006, China; School of Advanced Manufacturing, Guangdong University of Technology, Jieyang Center of Chemistry and Chemical Engineering Guangdong Laboratory, Jieyang 515200, China.
J Colloid Interface Sci. 2024 Dec;675:836-847. doi: 10.1016/j.jcis.2024.07.081. Epub 2024 Jul 10.
The persistent hurdles of charge rapid recombination, inefficient use of light and utilization of sacrificial reagents have plagued the field of photocatalytic hydrogen evolution (PHE). In this research, tiny MoO nanoparticles of 10 nm in diameter were prepared through a straightforward solvothermal approach with a specific ratio of oleylamine and oleic acid as stabilizers. The critical factor in the synthesis process was found to be the ratio of oleylamine to oleic acid. Moreover, a two-phase interface assembly method facilitated the uniform deposition of MoO onto CdS nanorods. Due to the localized plasmonic-thermoelectric effect on the surface of MoO along with its abundant oxygen vacancies, the composite catalyst exhibited outstanding photo-utilization efficiency and an abundance of active sites. The CdS-MoO composite displayed a unique photochemical property in transforming lactic acid into pyruvic acid and generating hydrogen simultaneously. After exposure to artificial sunlight for 4 h, significant values of 4.7 and 3.7 mmol⋅g⋅h were achieved for hydrogen production and pyruvic acid formation, respectively, exceeding CdS alone by 3.29 and 4.02-fold, while the selectivity of pyruvic acid was 95.68 %. Furthermore, the S-Scheme electron transport mechanism in the composites was elucidated using Electron Paramagnetic Resonance (EPR) spectroscopy, radical trapping experiments, energy band structure analysis, and the identification of critical intermediates in the process of selective oxidation. This work sheds light on the design and preparation of high-performance photocatalysts for biorefining coupled with efficient hydrogen evolution.
电荷快速复合、光利用效率低下以及牺牲试剂利用等长期存在的障碍一直困扰着光催化析氢（PHE）领域。在本研究中，通过一种简单的溶剂热法，以特定比例的油胺和油酸作为稳定剂，制备了直径为10 nm的微小MoO纳米颗粒。发现合成过程中的关键因素是油胺与油酸的比例。此外，一种两相界面组装方法促进了MoO在CdS纳米棒上的均匀沉积。由于MoO表面的局域等离子体 - 热电效应及其丰富的氧空位，该复合催化剂表现出出色的光利用效率和大量的活性位点。CdS - MoO复合材料在将乳酸转化为丙酮酸并同时产生氢气方面表现出独特的光化学性质。在人工阳光照射4小时后，产氢和丙酮酸生成的显著值分别达到4.7和3.7 mmol⋅g⋅h，分别比单独的CdS高出3.29倍和4.02倍，而丙酮酸的选择性为95.68%。此外，利用电子顺磁共振（EPR）光谱、自由基捕获实验、能带结构分析以及选择性氧化过程中关键中间体的鉴定，阐明了复合材料中的S型电子传输机制。这项工作为用于生物精炼并耦合高效析氢的高性能光催化剂的设计和制备提供了启示。
