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Converting CO₂to value‐added chemicals,e. g., CH₃OH, is highly desirable in terms of the carbon cycling while reducing CO₂emission from fossil fuel combustion. Cu‐based nanocatalysts are among the most efficient for selective CO₂‐to‐CH₃OH transformation; this conversion, however, suffers from low reactivity especially in the thermodynamically favored low temperature range. We herein report ultrasmall copper (Cu) nanocatalysts supported on crystalline, mesoporous zinc oxide nanoplate (Cu@mZnO) with notable activity and selectivity of CO₂‐to‐CH₃OH in the low temperature range of 200–250 °C. Cu@mZnO nanoplates are prepared based on the crystal‐crystal transition of mixed Cu and Zn basic carbonates to mesoporous metal oxides and subsequent hydrogen reduction. Under the nanoconfinement of mesopores in crystalline ZnO frameworks, ultrasmall Cu nanoparticles with an average diameter of 2.5 nm are produced. Cu@mZnO catalysts have a peak CH₃OH formation rate of 1.13 mol h⁻¹per 1 kg under ambient pressure at 246 °C, about 25 °C lower as compared to that of the benchmark catalyst of Cu−Zn−Al oxides. Our new synthetic strategy sheds some valuable insights into the design of porous catalysts for the important conversion of CO₂‐to‐CH₃OH.

 

Janus nanoparticles (NPs) containing two chemically distinct materials in one system are of great significance for catalysis in terms of harnessing catalytic synergies that are not exist in either component. We herein present a novel synthetic method of two Janus-type MnOx-Ag and MnOx-AgI NPs for efficient photochemical water oxidation. The synthesis of Janus-type MnOx-AgI NPs is based on the oxidative nucleation and growth of Ag domains on MnO first and the subsequent iodization of Ag. A mild and non-disruptive iodization strategy is developed to yield Janus MnOx-AgI NPs, in which converting Ag to AgI domains with iodomethane (CH3I) is achieved through the partial iodization. Simultaneously, Mn2+ species in the primary MnO octahedrons are oxidized during the growth of Ag NPs, leading to the formation of amorphous p-type MnOx domains. Therefore, as-resultant Janus-type MnOx-AgI NPs combining two semiconductors into an integrated nanostructure can be used as an efficient photocatalyst for visible light-driven water oxidation. Janus MnOx-AgI NPs show an expected photocatalytic activity even in the absence of Ru(bpy)3Cl2 as an electron mediator. This intriguing synthesis may open up a new opportunity to develop asymmetric nanostructures of two semiconductors that will potentially be efficient photocatalysts for solar-driven water splitting. 

Au is one of the most promising electrocatalysts to convert CO 2 into CO in an aqueous-phase electrochemical reduction. However, ultrasmall Au nanocatalysts (AuNCs, <2 nm) have proven to be favorable for water reduction over CO 2 , although they possess a large surface-to-volume ratio and potentially are ideal for CO 2 reduction. We herein report that ultrasmall AuNCs (1.9 ± 0.3 nm) supported on nitrided carbon are remarkably active and selective for CO 2 reduction. The mass activity for CO of AuNCs reaches 967 A g −1 with a faradaic efficiency for CO of ∼83% at −0.73 V ( vs . reversible hydrogen electrode) that is an order of magnitude more active than the state-of-the-art results. The high activity is endowed by the large surface area per unit weight and the high selectivity of ultrasmall AuNCs for CO 2 reduction originates from the cooperative effect of Au and the nitrided carbon support where the surface N sites act as Lewis bases to increase the surface charge density of AuNCs and enhance the localized concentration of CO 2 nearby catalytically active Au sites. We show that our results can be applied to other pre-synthesized Au catalysts to largely improve their selectivity for CO 2 reduction by 50%. Our method is expected to illustrate a general guideline to effectively lower the cost of Au catalysts per unit weight of the product while maintaining its high selectivity for CO 2 reduction.