No abstract

Ultrathin metal layers can be highly active carbon dioxide electroreduction catalysts, but may also be prone to oxidation. Here we construct a model of graphene confined ultrathin layers of highly reactive metals, taking the synthetic highly reactive tin quantum sheets confined in graphene as an example. The higher electrochemical active area ensures 9 times larger carbon dioxide adsorption capacity relative to bulk tin, while the highly-conductive graphene favours rate-determining electron transfer from carbon dioxide to its radical anion. The lowered tin–tin coordination numbers, revealed by X-ray absorption fine structure spectroscopy, enable tin quantum sheets confined in graphene to efficiently stabilize the carbon dioxide radical anion, verified by 0.13 volts lowered potential of hydroxyl ion adsorption compared with bulk tin. Hence, the tin quantum sheets confined in graphene show enhanced electrocatalytic activity and stability. This work may provide a promising lead for designing efficient and robust catalysts for electrolytic fuel synthesis.

Solar CO reduction efficiency is largely limited by poor photoabsorption, sluggish electron-hole separation, and a high CO activation barrier. Defect engineering was employed to optimize these crucial processes. As a prototype, BiOBr atomic layers were fabricated and abundant oxygen vacancies were deliberately created on their surfaces. X-ray absorption near-edge structure and electron paramagnetic resonance spectra confirm the formation of oxygen vacancies. Theoretical calculations reveal the creation of new defect levels resulting from the oxygen vacancies, which extends the photoresponse into the visible-light region. The charge delocalization around the oxygen vacancies contributes to CO conversion into COOH* intermediate, which was confirmed by in situ Fourier-transform infrared spectroscopy. Surface photovoltage spectra and time-resolved fluorescence emission decay spectra indicate that the introduced oxygen vacancies promote the separation of carriers. As a result, the oxygen-deficient BiOBr atomic layers achieve visible-light-driven CO reduction with a CO formation rate of 87.4 μmol g h , which was not only 20 and 24 times higher than that of BiOBr atomic layers and bulk BiOBr, respectively, but also outperformed most previously reported single photocatalysts under comparable conditions.