Computational models of adsorption at metal surfaces are often based on DFT and make use of the generalized gradient approximation. This likely implies the presence of sizable errors in the gas... Show moreComputational models of adsorption at metal surfaces are often based on DFT and make use of the generalized gradient approximation. This likely implies the presence of sizable errors in the gas-phase energetics. Here, we take a step closer toward chemical accuracy with a semiempirical method to correct the gas-phase energetics of PBE, PW91, RPBE, and BEEF-vdW exchange-correlation functionals. The proposed two-step method is tested on a data set of 27 gas-phase molecules belonging to the carbon cycle: first, the errors are pinpointed based on formation energies, and second, the respective corrections are sequentially applied to ensure the progressive lowering of the data set's mean and maximum errors. We illustrate the benefits of the method in electrocatalysis by a substantial improvement of the calculated equilibrium and onset potentials for CO2 reduction to CO on Au, Ag, and Cu electrodes. This suggests that fast and systematic gas-phase corrections can be devised to augment the predictive power of computational catalysis models. Show less
In this work, we study the synthesis of diphenyl carbonate (DPC) from phenol and CO on gold electrodes studied by means of in situ Fourier transform infrared spectroscopy (FTIR). The results show... Show moreIn this work, we study the synthesis of diphenyl carbonate (DPC) from phenol and CO on gold electrodes studied by means of in situ Fourier transform infrared spectroscopy (FTIR). The results show that, on gold electrodes, the formation of DPC is observed at potentials as low as 0.4 V vs Ag/AgCl, together with the formation of dimethyl carbonate (DMC) from the carbonylation of methanol that was used as a solvent. The spectroelectrochemical results also suggest that the formation of DPC occurs via the replacement of the methoxy groups from DMC with phenoxy groups from phenol and not directly by the carbonylation of phenol. Although this transesterification process is known to occur with heterogeneous catalysts, it has not been reported under electrochemical conditions. These are interesting findings, since the direct DPC production by carbonylation of phenol to DPC is usually performed with Pd-based catalysts. With this reaction scheme of transesterification happening under electrochemical conditions, other non-Pd catalysts could be used as well for one-step DPC production from phenol and CO. These findings give important mechanistic insights into this reaction and open up possibilities to an alternative process for the production of DPC. Show less
