中国科学院大连化物所王峰团队报道了原子分散钯和簇化钯协同促进光催化甲醇脱氢。相关研究成果于2024年8月20日发表在国际顶尖学术期刊《美国化学会杂志》。

单原子、团簇和颗粒形式的负载金属可以单独或共同影响负载型非均相催化剂的活性。虽然已经确定了负载金属对负载型光催化剂整体活性的单独贡献，但由于混合金属物种的不同光电特性，它们的联合活性被忽视了。

该文中，原子分散的Pd（Pd₁）和Pd簇被负载到CdS上，作为甲醇脱氢的氧化和还原位点。Pd₁取代Cd²⁺，形成甲醇氧化的空穴捕获态，并有助于光沉积Pd团簇的分散。因此，基于Pd含量，负载Pd₁和Pd簇的CdS上的甲醇脱氢具有1.14 s^-1的最高周转频率，并在优化的反应条件下，在452 nm处提供了87±1%的表观量子产率的H₂和HCHO。

该工作强调了负载金属对提高光催化活性的协同催化作用。

附：英文原文

Title: Photocatalytic Methanol Dehydrogenation Promoted Synergistically by Atomically Dispersed Pd and Clustered Pd

Author: Zhuyan Gao, Tiziano Montini, Junju Mu, Nengchao Luo, Emiliano Fonda, Paolo Fornasiero, Feng Wang

Issue&Volume: August 20, 2024

Abstract: Supported metal in the form of single atoms, clusters, and particles can individually or jointly affect the activity of supported heterogeneous catalysts. While the individual contribution of the supported metal to the overall activity of supported photocatalysts has been identified, the joint activity of mixed metal species is overlooked because of their different photoelectric properties. Here, atomically dispersed Pd (Pd1) and Pd clusters are loaded onto CdS, serving as oxidation and reduction sites for methanol dehydrogenation. The Pd1 substitutes Cd2+, forming hole-trapping states for methanol oxidation and assisting the dispersion of photodeposited Pd clusters. Therefore, methanol dehydrogenation on CdS with supported Pd1 and Pd clusters exhibits the highest turnover frequency of 1.14 s–1 based on the Pd content and affords H2 and HCHO with a similar apparent quantum yield of 87 ± 1% at 452 nm under optimized reaction conditions. This work highlights the synergistic catalysis of supported metal for improved photocatalytic activity.

DOI: 10.1021/jacs.4c06573

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c06573