Qiang Zhang

The photothermal pathway of converting carbon dioxide (CO₂) into hydrocarbons presents an effective and straightforward production for solar fuels. Nonetheless, the rational design of a robust solar-driven catalytic system for efficient CO₂ conversion remains a persistent challenge. In this work, we elaborately construct a multi-shell Au@Rh nanoantenna reactor for photothermal CO₂ methanation. The plasmonically active multi-shell Au structure serves as ‘antenna’, and the catalytically active Rh nanoparticle function as ‘reactor’. The reactor exhibits a superior CH₄ yield rate and nearly 100% selectivity in comparison with the other Au structures (single-shell and nanoparticle) and the kinds of active sites (Ru, Ir, and Co). The well-arranged Au nanoparticles in multi-shell structure provide the collective plasmon-coupled excitation, leading to the strong LSPR effect. Then, the antenna could convert the wide-spectrum solar energy to high surface temperature and enhanced electric field. The in-situ spectra and theoretical calculation indicate that the CO₂ methanation reaction in Au@Rh nanoantenna reactor follows the formyl pathway. The strong electro-proton coupling transfer ability of Au@Rh nanoantenna reactor contributes to the complex reaction pathway for CO₂ methanation. Especially, compared with Au catalyst, both the formation of COOH* intermediate and the key transformation from CO* to CHO* in Au@Rh nanoantenna reactor were promoted through the adequate supply of proton-electron pair and the strong interaction between Au and Rh sites. The ingenious design for nanoantenna reactor and the new findings in photothermal CO₂ methanation will inspire the development of mild hydrogenation for boosting CO₂-to-fuel conversion.

The efficient development of electrocatalysts for the nitrogen reduction reaction (NRR) under ambient conditions has been greatly challenging due to the high stability of the N≡N bond and the competitive interference from the hydrogen evolution reaction (HER). This work innovatively designs a graphitic carbon nitride substrate (g‐C ₁₆ N ₁₉ ) with a super‐large pore structure based on the self‐doping strategy and first‐principles calculations, and constructs TM@g‐C ₁₆ N ₁₉ (TM = Ti ∼ Au) single‐atom catalyst systems. By establishing a “Four‐Step” screening model, it is found that W@g‐C ₁₆ N ₁₉ exhibits the best NRR catalytic performance, with an ultralow limiting potential (U _L ) of ‐0.23 V. Combining electron structure analyses such as charge density difference, ICOHP value, Bader charge, and spin magnetic moment, the micro‐mechanism of W@g‐C ₁₆ N ₁₉ effectively activating the σ/π bonds of N ₂ molecules through strong d‐p orbital hybridization is revealed. Furthermore, based on the pH‐ and potential‐dependent adsorption‐free energy results calculated by the constant potential model, pH‐potential coupling analysis shows that the configuration has a decisive influence on activity: the E‐I/S‐V mode dominates in alkaline media, while the E‐O/S‐O pathway is predominant under acidic conditions. In the E‐I configuration, the energy barrier of the rate‐determining step (PDS) of NRR decreases with the decrease of the electrode potential; conversely, the energy barrier of the PDS of NRR in the E‐O/S‐V/S‐O configuration increases with the decrease of the electrode potential.

Two-dimensional (2D) materials with strong light absorption and high charge carrier transfer kinetics have drawn much attention in photoelectrochemical (PEC) water splitting. However, the efficient photoelectric conversion performances of monomer 2D materials are a crucial basis for developing novel designs of composite photoelectrodes. Herein, high-quality vertically aligned 2D SnS₂/FTO photoelectrodes were synthesized via a modified chemical vapor deposition (CVD) method, where the FTO substrates were slantedly placed downstream. Particularly, a 2D SnS₂/FTO photoanode synthesized at d = 8 cm and f = 70 sccm exhibits excellent transient photocurrent densities of about 4.6 (full spectrum) and 3.6 (λ ≥ 420 nm) mA cm^-2 at 1.23 V versus RHE under light illumination (AM 1.5G, 100 mW cm^-2) conditions. Besides, the optimal η_IPCE, η_APCE, and η_sep efficiencies are approximately 20.64, 21.41, and 77.1%, respectively, which are also significantly improved compared to those of other 2D SnS₂/FTO photoelectrodes. In the 2D SnS₂/FTO PEC water splitting system, the maximal theoretical evolution rates of hydrogen and oxygen are approximately 5.83 and 2.91 μmol cm^-2 h^-1, respectively, according to photocurrent density. The effective photoelectric properties of the 2D SnS₂/FTO photoanode are mainly attributed to the light trapping structure and high crystallinity of 2D SnS₂ nanosheets, which greatly promote incident photon harvesting, provide abundant reflecting pathways, and cooperate with rapid charge carrier transfer kinetics, thereby obviously enhancing photoelectric conversion capacity and oxidation dynamics rates for PEC water splitting. This work supplies the important basis and values for designing and constructing highly efficient SnS₂-based heterojunction photoelectrodes, which are conducive to developing more practical applications, such as optoelectronic devices, water splitting, wastewater treatment, pollutant degradation, and so on.

We conducted an upgrade prediction for NRR electrocatalysts on g-C ₁₆ N ₅ featuring the local coordinationof TM–N ₄ , with Mo@g-C ₁₆ N ₅ standing out. Using the constant-potential method and an implicit solvent model, we find the electric double-layer capacitance is key in modulating the kinetic barrier.

Multifunctional HER/OER/ORR activities via the modification of chalcogen ligands.