用于实现高性能热催化氧化还原反应的二茂铁功能化锆氧簇

The Zr(Ⅳ)ions are easily hydrolyzed to form oxides,which severely limits the discovery of new structures and applications of Zr-based compounds.In this work,three ferrocene(Fc)-functionalized Zr-oxo clusters(ZrOCs),Zr_(9)Fc_(6),Zr_(10)Fc_(6) and Zr_(12)Fc_(8) were synthesized through inhibiting the hydrolysis of Zr(Ⅳ)ions,which show increased nuclearity and regular structural variation.More importantly,these Fc-functionalized ZrOCs were used as heterogeneous catalysts for the transfer hydrogenation of levulinic acid(LA)and phenol oxidation reactions for the first time,and displayed outstanding catalytic activity.In particular,Zr_(12)Fc_(8) with the largest number of Zr active sites and Fc groups can achieve>95% yield for LAto-c-valerolactone within 4 h(130℃)and>98% yield for 2,3,6-trimethylphenol-to-2,3,5-trimethyl-pbenzoquinone within 30 min(80℃),showing the best catalytic performance.Catalytic characterization combined with theory calculations reveal that in the Fc-functionalized ZrOCs,the Zr active sites could serve as substrate adsorption sites,while the Fc groups could act as hydrogen transfer reagent or Fenton reagent,and thus achieve effectively intramolecular metal-ligand synergistic catalysis.This work develops functionalized ZrOCs as catalysts for thermal-triggered redox reactions.

Photothermal catalysis for CO_(2) conversion

The conversion of carbon dioxide into useful fuels or chemical feedstocks is of great importance for achieving carbon emission peak and carbon neutrality. The harvesting and conversion of solar energy will provide a sustainable and environmentally friendly energy source for human production and living.Very recently, photothermal catalysis has been proved to exhibit great advantages in reducing the reaction temperature, promoting the catalytic activity, and manipulating the reaction pathway in comparison with traditional thermal catalysis. In this review, we firstly introduced the fundamental mechanisms and categories of photothermal catalysis to understand the synergy or the difference between photochemical and thermochemical reaction pathways. Subsequently, the criteria and strategies for photothermal catalyst design are discussed in order to inspire the development of high-efficiency photothermal catalytic route by achieving intense absorption of broadband solar energy spectrum and high conversion capability of solar-to-heat. Recent progress in CO_(2)reduction achieved by photothermal catalysis was summarized in terms of production types. In the end, the future challenges and perspectives of photothermal catalytic CO_(2)reduction are presented. We hope that this review will not only deepen the understanding of photothermal catalysis, but also inspire the design, preparation and application of high-performance photothermal catalysts, aiming at alleviating non-renewable fossil energy consumption and carbon emissions for early carbon emission peak and carbon neutrality.