Highly Efficient and Selective Light-Driven Dry Reforming of Methane by a Carbon Exchange Mechanism.

Dry reforming of methane (DRM) is a promising technique for converting greenhouse gases (namely, CH4 and CO2) into syngas. However, traditional thermocatalytic processes require high temperatures and suffer from low selectivity and coke-induced instability. Here, we report high-entropy alloys loaded on SrTiO3 as highly efficient and coke-resistant catalysts for light-driven DRM without a secondary source of heating. This process involves carbon exchange between reactants (i.e., CO2 and CH4) and oxygen exchange between CO2 and the lattice oxygen of supports, during which CO and H2 are gradually produced and released. Such a mechanism deeply suppresses the undesired side reactions such as reverse water-gas shift reaction and methane deep dissociation. Impressively, the optimized CoNiRuRhPd/SrTiO3 catalyst achieves ultrahigh activity (15.6/16.0 mol gmetal-1 h-1 for H2/CO production), long-term stability (∼150 h), and remarkable selectivity (∼0.96). This work opens a new avenue for future energy-efficient industrial applications.

Ag2 S-CdS p-n Nanojunction-Enhanced Photocatalytic Oxidation of Alcohols to Aldehydes.

Selective oxidation of alcohols to aldehydes under mild conditions is important for the synthesis of high-value-added organic intermediates but still very challenging. For most of the thermal and photocatalytic systems, noble metal catalysts or harsh reaction conditions are required. Herein, the synthesis and use of Ag2 S-CdS p-n nanojunctions as an efficient photocatalyst for selective oxidation of a series of aromatic alcohols to their corresponding aldehydes is reported. High quantum efficiencies (59.6% and 36.9% under 380 and 420 nm, respectively) are achieved in air atmosphere at room temperature. Photoluminescence and photo-electrochemical tests show that the excellent performance is mainly due to the p-n junction-enhanced charge separation and transfer for the activation of both O2 (in air) and substrates. This study demonstrates the potential of p-n junction in photocatalytic synthesis under mild conditions.

Covalent Organic Frameworks with Chirality Enriched by Biomolecules for Efficient Chiral Separation.

The separation of racemic compounds is important in many fields, such as pharmacology and biology. Taking advantage of the intrinsically strong chiral environment and specific interactions featured by biomolecules, here we contribute a general strategy is developed to enrich chirality into covalent organic frameworks (COFs) by covalently immobilizing a series of biomolecules (amino acids, peptides, enzymes) into achiral COFs. Inheriting the strong chirality and specific interactions from the immobilized biomolecules, the afforded biomolecules⊂COFs serve as versatile and highly efficient chiral stationary phases towards various racemates in both normal and reverse phase of high-performance liquid chromatography (HPLC). The different interactions between enzyme secondary structure and racemates were revealed by surface-enhanced Raman scattering studies, accounting for the observed chiral separation capacity of enzymes⊂COFs.

Efficient Thermal Management with Selective Metamaterial Absorber for Boosting Photothermal CO2 Hydrogenation under Sunlight.

Photothermal catalytic CO2 hydrogenation is a prospective strategy to simultaneously reduce CO2 emission and generate value-added fuels. However, the demand of extremely intense light hinders its development in practical applications. Herein, this work reports the novel design of Ni-based selective metamaterial absorber and employs it as the photothermal catalyst for CO2 hydrogenation. The selective absorption property reduces the heat loss caused by radiation while possessing effectively solar absorption, thus substantially increasing local photothermal temperature. Notably, the enhancement of local electric field by plasmon resonance promotes the adsorption and activation of reactants. Moreover, benefiting from the ingenious morphology that Ni nanoparticles (NPs) are encapsulated by SiO2 matrix through co-sputtering, the greatly improved dispersion of Ni NPs enables enhancing the contact with reaction gas and preventing the agglomeration. Consequently, the catalyst exhibits an unprecedented CO2 conversion rate of 516.9 mmol gcat -1 h-1 under 0.8 W cm-2 irradiation, with near 90% CO selectivity and high stability. Significantly, this designed photothermal catalyst demonstrates the great potential in practical applications under sunlight. This work provides new sights for designing high-performance photothermal catalysts by thermal management.

Recent Advances in Porous Materials for Photocatalytic CO2 Reduction.

Photocatalytic CO2 reduction into solar fuels is a promising technology for addressing energy and CO2 emission issues. Because of the superior properties in CO2 adsorption and activation, molecular diffusion, light absorption, and charge separation and transfer, porous materials have been developed into a multifunctional platform for photocatalytic CO2 reduction. In this Perspective, we first discuss the emerging trends of CO2 reduction in major inorganic porous materials-based photocatalysts, such as mesoporous materials, macroporous materials, hollow materials, hierarchically porous materials, and zeolites. Prospects and challenges in the development of porous materials-based photocatalysts are then outlined. Finally, we envision feasible solutions for the deployment of porous materials to enhance photocatalytic CO2 reduction performance.

Plasmon-Enhanced Deuteration under Visible-Light Irradiation.

Deuteration has found important applications in synthetic chemistry especially for pharmaceutical developments. However, conventional deuteration methods using transition-metal catalysts or strong bases generally involve harsh reaction conditions, expensive deuterium source, insufficient efficiency, and poor selectivity. Herein, we report an efficient visible-light-driven dehalogenative deuteration of organic halides using plasmonic Au/CdS as photocatalyst and D2O as deuterium donor. Electron transfer from Au to CdS, which has been confirmed by surface-enhanced Raman spectroscopy, plays a decisive role for the plasmon-mediated dehalogenation. The deuteration is revealed to proceed via a radical pathway in which substrates are first activated by the photoinduced electron transfer to generate aryl radicals, and the radicals are further trapped by D2O to give deuterated products. Under visible-light irradiation, excellent deuteration efficiency is achieved with high functional group tolerance and a wide range of substrates at room temperature. Compared with bare CdS, the photocatalytic activity increases ∼18 times after the loading of plasmonic Au nanoparticles. This work sheds light on the interfacial charge transfer between plasmonic metals and semiconductors as an important criterion for rational design of visible-light photocatalysts.