Continuous synthesis of formic acid and methyl formate via CO2 hydrogenation is demonstrated using a molecular iridium complex stably immobilized on a solid covalent triazine framework (CTF) under high-pressure conditions. Compared to formic acid synthesis, methyl formate synthesis is advantageous to enhance the selectivity and yield of formates under kinetically favorable high temperature conditions. Transient in situ vibrational spectroscopy shows that the CTF strongly interacts with CO2 and H2, and even activates methanol. Hence, CTF is a promising support for molecular catalysts, even under harsh supercritical and flow conditions, through its strong binding capability.@en

Surface intermediate species and oxygen vacancy-assisted mechanism over CeO2 catalyst in the direct dimethyl carbonate (DMC) synthesis from carbon dioxide and methanol are suggested by means of transient spectroscopic methodologies in conjunction with multivariate spectral analysis. How the two reactants, i.e. CO2 and methanol, interact with the CeO2 surface and how they form decisive surface intermediates leading to DMC are unraveled by DFT-based molecular dynamics simulation by precise statistical sampling of various configurations of surface states and intermediates. The atomistic simulations and uncovered stability of different intermediate states perfectly explain the unique DMC formation profile experimentally observed upon transient operations, strongly supporting the proposed oxygen vacancy-assisted reaction mechanism.@en