Arne Thomas

Sustainable multicarbon e‐chemicals are of particular interest due to their potential future, high market values, and demand. In the direct electrocatalytic formation of multicarbon e‐chemicals from CO 2 , the elementary C–C coupling by CO dimerization is considered the rate‐limiting step. Here, a generalized surface structural design principle of asymmetric metal pair sites is proposed, explored, and experimentally tested in order to promote CO dimerization on surfaces. First a computational model of N‐doped Cu 2 S layers featuring adjacent, electronically asymmetric Cu δ1+ ‐Cu δ2+ (0 < δ 1 + < δ 2 + < 1) metal atomic pairs evidenced by their non‐uniform charge distribution is considered. The electronic asymmetry resulted in distinct CO adsorption energies and the associated self‐adjusting structures, which lowered C–C coupling energy barriers significantly. The computational hypotheses are experimentally tested using X‐ray photoelectron spectroscopy of Cu‐N moieties within N‐doped Cu 2 S layers. In‐situ Fourier‐transform infrared spectroscopy confirms linear *CO and *CO‐CO adsorption configuration by the peaks of ≈2080 and 1920 cm −1 , respectively. After N‐doping, the catalytically C 2 faradaic efficiency can significantly be elevated to 14.72% due to the promotion of C–C coupling.

The Wittig reaction is a key step in industrial processes to synthesise large quantities of vitamin A and various other important chemicals that are used in daily life. This article presents a pathway to achieve the Wittig reaction in a solid network. A highly porous triphenylphosphine‐based polymer was applied as a solid Wittig reagent that undergoes, in a multi‐step cycle, in total six post‐synthetic modifications. This allowed for regeneration of the solid Wittig reagent and reuse for the same reaction cycle. Of particular industrial relevance is that the newly developed material also enables a simple way of separating the product by filtration. Therefore, additional costly and difficult separation and purification steps are no longer needed.