Sort:
Research Article Issue
Molecular surface functionalization of In2O3 to tune interfacial microenvironment for enhanced catalytic performance of CO2 electroreduction
Nano Research 2024, 17 (3): 1242-1250
Published: 08 August 2023
Downloads:19

Indium-based materials (e.g., In2O3) are a class of promising non-noble metal-based catalysts for electroreduction of carbon dioxide (CO2). However, competitive hydrogen reduction reaction (HER) on indium-based catalysts hampers CO2 reduction reaction (CO2RR) process. We herein tune the interfacial microenvironment of In2O3 through chemical graft of alkyl phosphoric acid molecules using a facile solution-processed strategy for the first time, which is distinguished from other researches that tailor intrinsic activity of In2O3 themselves. The surface functionalization of alkyl phosphoric acids over In2O3 is demonstrated to remarkably boost CO2 conversion. For example, octadecylphosphonic acid modified In2O3 exhibits Faraday efficiency for H2 (FE H2) of as low as 6.6% and FEHCOOH of 86.5% at −0.67 V vs. RHE, which are far superior to parent In2O3 counterparts (FE H2 of 24.0% and FEHCOOH of 63.1%). Moreover, the enhancing effect of alkyl phosphoric acid functionalization is found to be closely related to the length of alkyl chains. By virtue of comprehensive experimental characterizations and molecular dynamics simulations, it is revealed that the modification of alkyl phosphoric acids significantly alters the interface microenvironment of the electrocatalyst, which changes the electrocatalyst surface from hydrophilic and aerophobic to hydrophobic and aerophilic. In this case, the water molecules are pushed away and more CO2 molecules are trapped, increasing local CO2 concentration at In2O3 active sites, thus leading to the significantly enhanced CO2RR and suppressed HER. This work highlights the importance of regulating the interfacial microenvironment of inorganic catalysts by molecular surface functionalization as a means for promoting the electrochemical performance in electrosynthesis and beyond.

Open Access Review Article Issue
Latest progress in covalently modified polyoxometalates-based molecular assemblies and advanced materials
Polyoxometalates 2022, 1 (2): 9140011
Published: 22 November 2022
Downloads:1396

Covalently modified polyoxometalates (POMs), which benefit from the synergistic effect between POMs and covalently grafted moieties, have received increasing attention in various fields. Recent studies on covalently modified POMs mainly focus on function-directed POM assemblies. This review summarizes the latest progress (2017–2022) concerning covalently modified POMs from a functional perspective, which can be classified as assembly chemistry, photochemistry, electrochemistry, homogeneous and heterogeneous catalysis, and biological applications. The roles of POMs and covalently grafted moieties in these hybrids, especially the rational design for specific applications, were considered and emphasized.

total 2