Haffner Ádám, Höltzl Tibor
Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Műegyetem rkp. 3., H1111, Budapest, Hungary.
HUN-REN-BME Computation Driven Chemistry Research Group, Budapest University of Technology and Economics, Műegyetem rkp. 3., H1111, Budapest, Hungary.
Chempluschem. 2025 Aug;90(8):e202500223. doi: 10.1002/cplu.202500223. Epub 2025 Jul 8.
Enhancing efficiency and product selectivity presents a significant challenge in carbon dioxide electroreduction (CORR). Recent studies have demonstrated that the solvent in the electrolyte plays a crucial role; however, its specific functions are being investigated intensively. The study utilizes hierarchically assembled models, enabling to decoupling of the various effects of the solvent. Both (sub)nanoclusters and surfaces with adatoms are utilized as model systems, which allow to study the effect of the solvent on the low-coordinated reaction sites. It is observed that water binds to the low-coordination active sites of the catalytic centers, thereby influencing the reaction mechanism. This binding leads to significant charge transfer between the solvent and the catalyst, altering its charge state and the potential of zero charge-both of which are known to affect product selectivity. Additionally, a solvent-induced reorganization of the catalyst structure that can substantially influence reduction processes is observed. The solvation and solubility of the adsorbates also play a significant role, as they influence the desorption of the possible products from the catalyst surface. Thus, the hierarchy of models presented here enables a systematic understanding of the microscopic role of solvents and paves the way for computational solvent engineering to optimize product selectivity in CORR.
提高效率和产物选择性是二氧化碳电还原（CORR）中的一项重大挑战。最近的研究表明，电解质中的溶剂起着至关重要的作用；然而，其具体功能仍在深入研究中。该研究利用分层组装模型，能够分离溶剂的各种效应。（亚）纳米团簇和带有吸附原子的表面都被用作模型系统，这使得能够研究溶剂对低配位反应位点的影响。据观察，水与催化中心的低配位活性位点结合，从而影响反应机理。这种结合导致溶剂与催化剂之间发生显著的电荷转移，改变其电荷状态和零电荷电位——这两者都已知会影响产物选择性。此外，还观察到溶剂诱导的催化剂结构重组，这可能会对还原过程产生重大影响。吸附质的溶剂化和溶解度也起着重要作用，因为它们会影响可能产物从催化剂表面的解吸。因此，这里提出的模型层次结构能够系统地理解溶剂的微观作用，并为通过计算溶剂工程优化CORR中的产物选择性铺平了道路。
