Search

Photocatalytic conversion of CO 2 to chemical feedstocks represents an intriguing approach to address the energy and environmental crisis, but faces low conversion efficiencies resulted from unsatisfied light absorption, charge recombination and surface reactivity of traditional semiconductor photocatalysts. Herein, we report stacked graphene/Pd@PtCu nanostructures with atomically thin PtCu shell to overcome above challenges and realize high-efficient CO 2 -to-CH 4 photoreduction. The smart design begins with the excitation of Ru complex with broad visible absorption, which is followed by the smooth movement of photoelectrons via the graphene→Pd→PtCu pathway, and then the highly selective CO 2 reduction on the PtCu surface. As the PtCu thickness decreases, the strengthened Pd–PtCu interfacial charge polarization contributes to improved charge separation/migration. Meanwhile, CO 2 adsorption on the PtCu surface is ameliorated owing to increased electron accumulation and compressive strain. This work provides a new design for boosting the photocatalytic performance by cooperative surface and interfacial modulations. [Display omitted] • Stacked graphene/Pd@PtCu structures with atomically thin PtCu shell are fabricated. • Pd–PtCu interfacial charge polarization promotes the charge separation and transfer. • Increased electron density and lattice strain enhance the CO2 adsorption on PtCu surface. • Photoreduction of CO 2 to CH 4 with high activity, selectivity and stability is reached. [ABSTRACT FROM AUTHOR]

[Display omitted] • CsPbBr 3 nanocubes, nanorods and nanowires are deposited on 2D NMF, respectively. • The 2D NMF as cocatalyst improves the photocatalytic activity in CO 2 -to-CO conversion. • The photocatalytic enhancement is greatly dependent on the aspect ratio of CsPbBr 3. • The elongation of CsPbBr 3 enlarges the ΔE of CB and improves the charge separation. All-inorganic CsPbBr 3 perovskites have been regarded as promising candidates for photocatalytic CO 2 reduction, but the conversion efficiency is limited by serious charge recombination and poor surface reactivity. Herein, a two-dimensional Ni based metal-organic framework (NMF) has been employed as a cocatalyst, which not only acts as an electron extractor in enhancing the electron-hole separation, but also serves as a CO 2 capturing agent in facilitating the adsorption and activation of CO 2 molecules. As a result, 1.8, 2.5 and 4.1-fold enhancement in CO production has been realized for CsPbBr 3 nanocubes, nanorods and nanowires, respectively, which is proved to be positively correlated with the aspect ratio of CsPbBr 3. The aspect ratio dependent photocatalytic enhancement is attributed to the increased energy difference at the interface between the conduction band of CsPbBr 3 and NMF with the elongation of CsPbBr 3 , which produces an enlarged driving force for promoted interfacial electron transfer and superior charge separation properties. [ABSTRACT FROM AUTHOR]