Efficient Alkene Hydroformylation by Co-C Symmetry-Breaking Sites.

Alkene hydroformylation is one of the largest industrial reactions on an industrial scale; however, the development of nonnoble heterogeneous catalysts is usually limited by their low activities and stabilities. Herein, we constructed a 1% Co2C/SiO2 catalyst featuring Co-Cvacancy-Co-C symmetry-breaking sites, which generated a polar surface exhibiting a moderate charge density gradient at the localized Co atoms. Comparatively, this catalyst exhibited notable enhancements in the adsorption and activation of the reactants, as well as in the polarity between intermediates. Significantly, the spatial distance between the adsorption sites of intermediates was reduced, thereby effectively decreasing the energy barrier of reaction processes. As the density of the symmetry-breaking sites increased, the turnover number for propene hydroformylation soared to 18 363, exceeding the activity of heterogeneous Co-based catalysts reported thus far by 1 or 2 orders of magnitude, and the catalyst exhibited high stability during the reaction. This study provides a methodology for constructing atomically active sites, which holds great potential for the design and development of highly efficient catalysts.

Selective Production of Linear Aldehydes and Alcohols from Alkenes using Formic Acid as Syngas Surrogate.

Performing carbonylation without the use of carbon monoxide for high-value-added products is an attractive yet challenging topic in sustainable chemistry. Herein, effective methods for producing linear aldehydes or alcohols selectively with formic acid as both carbon monoxide and hydrogen source have been described. Linear-selective hydroformylation of alkenes proceeds smoothly with up to 88 % yield and >30 regioselectivity in the presence of single Rh catalyst. Strikingly, introducing Ru into the system, the dual Rh/Ru catalysts accomplish efficient and regioselective hydroxymethylation in one pot. The present processes utilizing formic acid as syngas surrogate operate simply under mild condition, which opens a sustainable way for production of linear aldehydes and alcohols without the need for gas cylinders and autoclaves. As formic acid can be readily produced via CO2 hydrogenation, the protocols represent indirect approaches for chemical valorization of CO2 .

Effectively Regulating the Microenvironment of Atomically Dispersed Rh through Co and Pi to Promote the Selectivity in Olefin Hydroformylation.

In the study of heterogeneity of homogeneous processes, effective control of the microenvironment of active sites is a reliable means to improve the selectivity of products. Here, we develop a high-performance Rh-based atomically dispersed catalyst for olefin hydroformylation by controlling the electronic environment and spatial distribution of active metals on the supports, which is achieved through wet impregnation of Rh on ZnO modified with Pi and Co. Various characterizations demonstrate that Co weakens Rh-CO interactions and Pi promotes the formation of atomically dispersed Rh, which thereby improves the selectivity of linear aldehydes in hydroformylation. This strategy of rationally designing the local microenvironment of active metals is important to optimize the catalytic performance.