清华大学王训团队开发了多金属氧酸盐夹层的Zn金属酞菁分子层三明治结构作为光偶联电催化CO₂还原催化剂。相关研究成果于2021年8月24日发表在国际顶尖学术期刊《美国化学会杂志》。

开发高效、稳定的非均相金属酞菁电催化剂用于CO₂还原仍然是一个挑战。

该文提出了锌-金属酞菁（MPc）分子层/多金属氧酸盐（POM）三明治层状材料的通用合成方法，从而提高了电催化和光耦电催化CO₂还原的性能。POM的加入可以防止MPc分子层的聚集，有利于活性中心的暴露。分子层三明治催化剂表现出优异的CO₂还原活性，在相对0.7 V（vs RHE）条件下，在暗场中提供最高的CO法拉第效率（FECO），达到96.1%。在光照下，FECO在0.6-0.9V（vs RHE）的宽电位范围内达到93%以上，最大值为96.2%，一氧化碳转换频率可超过2060h^–1。

光电化学测试和发光表征表明，分子层有利于光照下的载流子分离；密度泛函理论计算和电子顺磁共振表明，外部光场对催化性能有2倍的增强作用。

附：英文原文

Title: Polyoxometalate Interlayered Zinc–Metallophthalocyanine Molecular Layer Sandwich as Photocoupled Electrocatalytic CO2 Reduction Catalyst

Author: Haozhou Yang, Deren Yang, Yue Zhou, Xun Wang

Issue&Volume: August 24, 2021

Abstract: Developing efficient and robust heterogeneous metallophthalocyanine electrocatalysts for CO2 reduction remains a challenge. Here, a general synthetic method of zinc–metallophthalocyanine (MPc) molecular layer/polyoxometalate (POM) sandwich lamellar material is developed, and thus improved performance of electrocatalytic and photocoupled electrocatalytic CO2 reduction is achieved. The incorporation of POM could prevent the packing of MPc molecular layers from aggregation, which would be favorable to the exposure of active sites. The molecular layer sandwich catalyst presents superior CO2 reduction activity, delivering the highest CO Faradaic efficiency (FECO) of 96.1% at 0.7 V vs RHE in dark field. Under light irradiation, over 93% FECO is achieved in a broad potential range from 0.6 to 0.9 V vs RHE with a maximum of 96.2%, and the carbon monoxide turnover frequency could exceed 2060 h–1. Photoelectrochemical tests and luminescence characterizations reveal the molecular layer is beneficial for carrier separation during light irradiation; density functional theory calculations and electron paramagnetic resonance indicated a 2-fold enhancement of the external light field on the catalytic performance.

DOI: 10.1021/jacs.1c05580

Source: https://pubs.acs.org/doi/10.1021/jacs.1c05580