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.

Continuous Flow System for Highly Efficient and Durable Photocatalytic Oxidative Coupling of Methane.

Photocatalytic oxidative coupling of methane (OCM) into value-added industrial chemicals offers an appealing green technique for achieving sustainable development, whereas it encounters double bottlenecks in relatively low methane conversion rate and severe overoxidation. Herein, we engineer a continuous gas flow system to achieve efficient photocatalytic OCM while suppressing overoxidation by synergizing the moderate active oxygen species, surface plasmon-mediated polarization, and multipoint gas intake flow reactor. Particularly, a remarkable CH4 conversion rate of 218.2 µmol h-1 with an excellent selectivity of ∼90% toward C2+ hydrocarbons and a remarkable stability over 240 h is achieved over a designed Au/TiO2 photocatalyst in our continuous gas flow system with a homemade three-dimensional (3D) printed flow reactor. This work provides an informative concept to engineer a high-performance flow system for photocatalytic OCM by synergizing the design of the reactor and photocatalyst to synchronously regulate the mass transfer, activation of reactants, and inhibition of overoxidation.

Rational Design of N-Doped Carbon-Coated Cobalt Nanoparticles for Highly Efficient and Durable Photothermal CO2 Conversion.

Photothermal CO2 hydrogenation to high-value-added chemicals and fuels is an appealing approach to alleviate energy and environmental concerns. However, it still relies on the development of earth-abundant, efficient, and durable catalysts. Here, the design of N-doped carbon-coated Co nanoparticles (NPs), as a photothermal catalyst, synthesized through a two-step pyrolysis of Co-based ZIF-67 precursor, is reported. Consequently, the catalyst exhibits remarkable activity and stability for photothermal CO2 hydrogenation to CO with a 0.75 mol gcat -1 h-1 CO production rate under the full spectrum of light illumination. The high activity and durability of these Co NPs are mainly attributed to the synergy of the attuned size of Co NPs, the thickness of carbon layers, and the N doping species. Impressively, the experimental characterizations and theoretical simulations show that such a simple N-doped carbon coating strategy can effectively facilitate the desorption of generated CO and activation of reactants due to the strong photothermal effect. This work provides a simple and efficient route for the preparation of highly active and durable nonprecious metal catalysts for promising photothermal catalytic reactions.

A Stacked Plasmonic Metamaterial with Strong Localized Electric Field Enables Highly Efficient Broadband Light-Driven CO2 Hydrogenation.

Light utilization largely governs the performance of CO2 photoconversion, whereas most of the materials that are implemented in such an application are restricted in a narrow spectral absorption range. Plasmonic metamaterials with a designable regular pattern and facile tunability are excellent candidates for maximizing light absorption to generate substantial hot electrons and thermal energy. Herein, a concept of coupling a Au-based stacked plasmonic metamaterial with single Cu atoms in alloy, as light absorber and catalytic sites, respectively, is reported for gas-phase light-driven catalytic CO2 hydrogenation. The metamaterial structure works in a broad spectral range (370-1040 nm) to generate high surface temperature for photothermal catalysis, and also induces strong localized electric field in favor of transfer of hot electrons and reduced energy barrier in CO2 hydrogenation. This work unravels the significant role of a strong localized electric field in photothermal catalysis and demonstrates a scalable fabrication approach to light-driven catalysts based on plasmonic metamaterials.

Tuning the local electronic structure of a single-site Ni catalyst by co-doping a 3D graphene framework with B/N atoms toward enhanced CO2 electroreduction.

Various single metal sites supported on N-doped carbon materials have been demonstrated to be effective catalysts for CO2 electroreduction. However, it remains a challenging task to gain comprehensive understanding on how the local electronic structures of single metal catalytic sites are rationally tuned, which eventually holds the key to significantly enhance the electrocatalytic performance. Herein, we implement B-N bonds into an N-doped 3D graphene framework by B doping to further stabilize the supported catalytic Ni single-sites and simultaneously tune their local electronic structure. Moreover, electrochemical in situ Fourier-transform infrared spectroscopy reveals that the B-N bonds can further facilitate the production of pivotal *COOH intermediates in comparison with only N doping. As a result, the Ni single-site catalyst on the B, N co-doped 3D graphene framework achieves excellent catalytic performance with a CO faradaic efficiency (FE) of 98% and a turnover frequency (TOF) value of 20.1 s-1 at -0.8 V (vs. RHE), whereas the FE and TOF for the control sample without B doping are as low as 62% and 6.0 s-1, respectively. This work highlights the superiority of modulating local electronic structures of single-site catalysts toward efficient electrocatalytic CO2 reduction.