Heterogeneous Photocatalytic C(sp)-H Activation of Formate for Hydrocarboxylation of Alkenes.

Light-driven carboxylation offers a promising approach for synthesizing valuable fine chemicals under mild conditions. Here we disclose a heterogeneous photocatalytic strategy of C(sp)-H activation of formate for hydrocarboxylation of alkenes over zinc indium sulfide (ZnInS) under visible light. This protocol functions well with a variety of substituted styrenes with good to excellent yields; it also works for unactivated alkenes albeit with lower yields.

Heterogeneous Photocatalytic Strategies for C(sp )-H Activation.

Activation of ubiquitous C(sp )-H bonds is extremely attractive but remains a great challenge. Heterogeneous photocatalysis offers a promising and sustainable approach for C(sp )-H activation and has been fast developing in the past decade. This Minireview focuses on mechanism and strategies for heterogeneous photocatalytic C(sp )-H activation.

A Multiscale, Dynamic Elucidation of Li Solubility in the Alloy and Metallic Plating Process.

Li-containing alloys and metallic deposits offer substantial Li storage capacities as alternative anodes to commercial graphite. However, the thermodynamically in sequence, yet kinetically competitive mechanism between Li solubility in the solid solution and intermediate alloy-induced Li deposition remains debated, particularly across the multiple scales. The elucidation of the mechanism is rather challenging due to the dynamic alloy evolution upon the non-equilibrium, transient lithiation processes under coupled physical fields.

Photo-thermal Cooperative Carbonylation of Ethanol with CO on Cu O-SrTiCuO.

Carbonylation of ethanol with CO as carbonyl source into value-added esters is of considerable significance and interest, while remains of great challenge due to the harsh conditions for activation of inert CO in that the harsh conditions result in undesired activation of α-C-H and even cleavage of C-C bond in ethanol to deteriorate the specific activation of O-H bond. Herein, we propose a photo-thermal cooperative strategy for carbonylation of ethanol with CO , in which CO is activated to reactive CO via photo-catalysis with the assistance of *H from thermally-catalyzed dissociation of alcoholic O-H bond. To achieve this proposal, an interfacial site and oxygen vacancy both abundant SrTiCuO supported Cu O (Cu O-SrTiCuO ) has been designed.

Mesoscale Mechanism of P-dopant Defects and Interface Synergy for Phenols Degradation.

The semiconductor based photocatalysis has become a hot spot of current research, and the key challenges are the construction of strong functional heterojunction photocatalysts, and insights on the working mechanism involved. In this work, we constructed a NiFe- LDHs/P-TCN heterojunction with P-dopant defects and interface synergy and elucidated its mesoscale mechanism among different constituent interfaces. The interface photoelectron transfer was detected by PAS, EPR and other methods, and the enhancing mechanism of the defect sites for interface electron transfer and photocatalytic activity was proposed.

Light-Induced Redox Looping of a Rhodium/Ce WO Photocatalyst for Highly Active and Robust Dry Reforming of Methane.

Dry reforming of methane (DRM) has provided an effective avenue to convert two greenhouse gases, CH and CO , into syngas. Here, we design a DRM photocatalyst Rh/Ce WO that invokes both photothermal and photoelectric processes, which overcomes the thermodynamic limitation of DRM under conventional conditions. In contrast to plasmonic or UV-response photocatalysts, our photocatalyst produces a superior light-to-chemical energy efficiency (LTCEE) of 4.

Selective Photocatalytic Activation of Ethanol C-H and O-H Bonds over Multi-Au@SiO/TiO: Role of Catalyst Surface Structure and Reaction Kinetics.

The chemical bond diversity and flexible reactivity of biomass-derived ethanol make it a vital feedstock for the production of value-added chemicals but result in low conversion selectivity. Herein, composite catalysts comprising SiO-coated single- or multiparticle Au cores hybridized with TiO nanoparticles (mono- or multi-Au@SiO/TiO, respectively) were fabricated via electrostatic self-assembly. The C-H and O-H bonds of ethanol were selectively activated (by SiO and TiO, respectively) under irradiation to form CHCH(OH) or CHCHO radicals, respectively.

Light-Driven Alcohol Splitting by Heterogeneous Photocatalysis: Recent Advances, Mechanism and Prospects.

Splitting of alcohols into hydrogen and corresponding carbonyl compounds, also called acceptorless alcohol dehydrogenation, is of great significance for both synthetic chemistry and hydrogen production. Light-Driven Alcohol Splitting (LDAS) by heterogeneous photocatalysis is a promising route to achieve such transformations, and it possesses advantages including high selectivity of the carbonyl compounds, extremely mild reaction conditions (room temperature and irradiation of visible light) and easy separation of the photocatalysts from the reaction mixtures. Because a variety of alcohols can be derived from biomass, LDAS can also be regarded as one of the most sustainable approaches for hydrogen production.

Photothermal-enhanced catalysis in core-shell plasmonic hierarchical CuS microsphere@zeolitic imidazole framework-8.

Conventional semiconductor photocatalysis based on band-edge absorption remains inefficient due to the limited harvesting of solar irradiation and the complicated surface/interface chemistry. Herein, novel photothermal-enhanced catalysis was achieved in a core-shell hierarchical CuS nano-heater@ZIF-8 heterostructures near-infrared localized surface plasmon resonance. Our results demonstrated that both the high surface temperature of the photothermal CuS core and the close-adjacency of catalytic ZIF-8 shell contributed to the extremely enhanced catalytic activity.

Efficient Visible Light-Driven Splitting of Alcohols into Hydrogen and Corresponding Carbonyl Compounds over a Ni-Modified CdS Photocatalyst.

Splitting of alcohols into hydrogen and corresponding carbonyl compounds has potential applications in hydrogen production and chemical industry. Herein, we report that a heterogeneous photocatalyst (Ni-modified CdS nanoparticles) could efficiently split alcohols into hydrogen and corresponding aldehydes or ketones in a stoichiometric manner under visible light irradiation. Optimized apparent quantum yields of 38%, 46%, and 48% were obtained at 447 nm for dehydrogenation of methanol, ethanol, and 2-propanol, respectively.

Catalyst-Free Growth of Three-Dimensional Graphene Flakes and Graphene/g-C₃N₄ Composite for Hydrocarbon Oxidation.

Mass production of high-quality graphene flakes is important for commercial applications. Graphene microsheets have been produced on an industrial scale by chemical and liquid-phase exfoliation of graphite. However, strong-interaction-induced interlayer aggregation usually leads to the degradation of their intrinsic properties.