Department of Chemistry and Biochemistry, Utah State University , Logan, Utah 84322, United States.
Centre for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology , Shanghai 200237, China.
J Am Chem Soc. 2017 Nov 8;139(44):15584-15587. doi: 10.1021/jacs.7b08657. Epub 2017 Oct 25.
Photocatalytic upgrading of crucial biomass-derived intermediate chemicals (i.e., furfural alcohol, 5-hydroxymethylfurfural (HMF)) to value-added products (aldehydes and acids) was carried out on ultrathin CdS nanosheets (thickness ∼1 nm) decorated with nickel (Ni/CdS). More importantly, simultaneous H production was realized upon visible light irradiation under ambient conditions utilizing these biomass intermediates as proton sources. The remarkable difference in the rates of transformation of furfural alcohol and HMF to their corresponding aldehydes in neutral water was observed and investigated. Aided by theoretical computation, it was rationalized that the slightly stronger binding affinity of the aldehyde group in HMF to Ni/CdS resulted in the lower transformation of HMF to 2,5-diformylfuran compared to that of furfural alcohol to furfural. Nevertheless, photocatalytic oxidation of furfural alcohol and HMF under alkaline conditions led to complete transformation to the respective carboxylates with concomitant production of H.
在超薄 CdS 纳米片（厚度约为 1nm）上负载镍（Ni/CdS），对关键的生物质衍生中间体化学品（糠醛醇、5-羟甲基糠醛（HMF））进行光催化升级，以制备附加值产品（醛和酸）。更重要的是，利用这些生物质中间体作为质子源，在可见光照射下，在环境条件下可以同时实现氢气的产生。在中性水中，观察到并研究了糠醛醇和 HMF 转化为相应醛的速率的显著差异。通过理论计算，合理地解释了 HMF 中醛基与 Ni/CdS 之间略微更强的结合亲和力，导致 HMF 向 2,5-二糠醛的转化率低于糠醛醇向糠醛的转化率。然而，在碱性条件下，糠醛醇和 HMF 的光催化氧化导致各自的羧酸盐完全转化，并伴随着氢气的产生。
