Na-Ru bimetallic functional sites promote photo-driven CO2 directed conversion into CH4.

Recently, there has been a significant increase in interest in using photocatalysis for the energy conversion of polluting gases. In this research, sodium and ruthenium bimetallic functional sites co-modified bismuth tungstate (Ru/Na-Bi2WO6) nanoflower photocatalyst was synthesized via the hydrothermal method. The CO2 reduction products on the Bi2WO6 substrate were CO (1.66 µmol/g/h, 68 %) and CH4 (0.78 µmol/g/h, 32 %). After optimization, a significant change in the CO2 products of the Bi2WO6-based composite material was observed, with CO (0.61 µmol/g/h, 3.6 %) and CH4 (16.1 µmol/g/h, 96.4 %). Results showed that the dominance of CH4 as the main product in the Ru/Na-BWO system is attributed to the effective doping of Na, which generates impurity energy levels composed of oxygen vacancies, lowering the conduction band position of Bi2WO6, thereby suppressing CO generation, and enhancing CH4 selectivity by changing the CO2 activation pathway. The remarkable performance is ascribed to the synergized adsorption and activation of CO2 by the tandem Na+ sites and Ru0 sites. Specifically, the doped Na+ sites play a major role in promoting the adsorption CO2 molecules, while the Ru0 sites play a dominant role in facilitating the activation of the intermediates.

Highly Efficient and Selective Photocatalytic Nonoxidative Coupling of Methane to Ethylene over Pd-Zn Synergistic Catalytic Sites.

Photocatalytic nonoxidative coupling of CH4 to multicarbon (C2+) hydrocarbons (e.g., C2H4) and H2 under ambient conditions provides a promising energy-conserving approach for utilization of carbon resource. However, as the methyl intermediates prefer to undergo self-coupling to produce ethane, it is a challenging task to control the selective conversion of CH4 to higher value-added C2H4. Herein, we adopt a synergistic catalysis strategy by integrating Pd-Zn active sites on visible light-responsive defective WO3 nanosheets for synergizing the adsorption, activation, and dehydrogenation processes in CH4 to C2H4 conversion. Benefiting from the synergy, our model catalyst achieves a remarkable C2+ compounds yield of 31.85 µmol·g-1·h-1 with an exceptionally high C2H4 selectivity of 75.3% and a stoichiometric H2 evolution. In situ spectroscopic studies reveal that the Zn sites promote the adsorption and activation of CH4 molecules to generate methyl and methoxy intermediates with the assistance of lattice oxygen, while the Pd sites facilitate the dehydrogenation of methoxy to methylene radicals for producing C2H4 and suppress overoxidation. This work demonstrates a strategy for designing efficient photocatalysts toward selective coupling of CH4 to higher value-added chemicals and highlights the importance of synergistic active sites to the synergy of key steps in catalytic reactions.