Xin Wang

Manipulating oriented electron flow and tailored reaction microenvironments in radial-unguided two-dimensional phosphorene remains challenging. Here, we show that Rh-decorated violet/black phosphorus heterostructures, engineered with integrative dual-electric fields from cooperative phase and fringing electric field, enable efficient vapor-fed photocatalytic hydrogen production. This dual-electric field establishes a strong intrinsic charge driving force and edge charge ordering. The vapor-fed gas–solid system minimizes interfacial diffusion barriers and solvent shielding, allowing the field to steer photoelectrons and interact with H₂O molecules at the edge-located Rh active centers. Analyses reveal that the integrative dual-electric field strengthens polarization and overcomes the water dissociation barrier at the gas–solid interface. The optimized catalyst achieves a H₂-generation rate of 5218.7 μmol g⁻¹ h⁻¹ under simulated sunlight, roughly 2.4 times conventional liquid–solid systems. This work demonstrates that synergy between integrative dual-electric fields and the gas–solid microenvironment overcome the kinetic limitations of phosphorene-based photocatalysts for efficient solar-driven hydrogen conversion.

To address the limitations of inefficient charge separation and imbalanced reaction intermediate adsorption that are inherent to the highly symmetric coordination structures of single-atom catalysts (SACs), a selective phosphorization strategy was developed for the precise construction of distorted asymmetric FeP3C1-coordinated Fe SACs on graphitic carbon nitride (g-C3N4). Through careful control of the phosphorization duration to regulate the phosphorus doping levels, tailored modulation was achieved for both the local dipole moments and the charge distributions at the Fe sites. Integrated experimental characterization and density functional theory calculations demonstrated that the distorted asymmetric FeP3C1 configuration significantly enhanced interfacial dipole moments, accelerating photogenerated charge separation while broadening the visible-light absorption. More importantly, the dipole-induced asymmetric charge distribution optimized the adsorption behavior of hydrogen intermediates, thereby lowering the Gibbs free energy barrier for the hydrogen evolution reaction (HER) and driving it toward the thermodynamic optimum. The FeP3C1/g-C3N4 exhibited an exceptional performance in the absence of noble-metal co-catalysts, achieving an HER rate of 7044.72 μmol g-1 h-1 and a peak apparent quantum efficiency of 12.87% at 380 nm. This work therefore establishes distortion-driven asymmetric coordination engineering and the associated dipole moment enhancement as a new paradigm for the design of efficient solar-to-hydrogen conversion catalysts.

Manipulating the oriented electron flow and tailored reaction microenvironments in radial-unguided 2D phosphorene remains challenging. Herein, Rh-decorated 2D/2D violet/black phosphorus (VP/BP-Rh) is engineered using integrative dual-electric fields (DEF) generated through cooperative phase electric field (PEF) and fringing electric field (FEF) to guide oriented charge flow and accurate catalytic centers. While the DEF establishes a powerful intrinsic charge driving force and edge charge ordering, its full potential is optimally unleashed in a vapor-fed gas–solid system. This unique system minimizes interfacial diffusion barriers and solvent shielding effects, allowing the DEF to steer photoelectrons and synergize with H₂O molecules exclusively and efficiently at the edge-located Rh active centers. Experimental and theoretical analyses reveal that the integrative DEF not only strengthens polarization but also ingeniously overcomes the water dissociation barrier at the gas-solid interfaces, significantly reducing the Gibbs free energy barrier for the vapor-to-hydrogen conversion. The resulting VP/BP-Rh achieves a record H₂-generation rate of 5218.7 µmol g⁻¹ h⁻¹ under simulated sunlight, marking ca. 2.4-fold improvement over conventional liquid–solid systems. This study highlights the key role of synergy between the integrative DEF and the gas–solid reaction microenvironment in solving the kinetic bottlenecks of 2D phosphorene-based photocatalysts for efficient solar-driven vapor-to-hydrogen conversion.

Developing biomimetic catalysts that replicate the nitrogenase functionality for ambient‐condition NH ₃ synthesis is a key goal of catalysis research. Recently, the enzymatic pathway with “side‐on” N ₂ adsorption is proposed for efficient photocatalytic N ₂ fixation. The “side‐on” mode involves the simultaneous bonding of both N atoms to active sites, enabling the enzymatic pathway with strong N ₂ adsorption and low energy barrier. Here, recent advances in photocatalytic N ₂ fixation via the enzymatic pathway are reviewed in terms of material design and reaction mechanism. The feasibility of regulating the N ₂ ‐fixation reaction pathway is demonstrated by summarizing the latest research on defect regulation, doping strategies, and surface engineering used to realize the enzymatic pathway. The effects of the N ₂ adsorption mode, charge transfer kinetics, and Gibbs free energy on photocatalytic N ₂ fixation via the enzymatic pathway are then comprehensively analyzed to elucidate the relationship between the reaction pathway and N ₂ fixation performance, which offers insights into the design of novel photocatalysts. Finally, an outlook on the challenges and future developments related to the enzymatic pathway of photocatalytic N ₂ fixation is presented. Bridging material innovation with mechanistic insights can accelerate the realization of practical photocatalytic systems for N ₂ fixation through the enzymatic pathway.

Photocatalytic nitrogen (N₂) fixation over semiconductors has always suffered from poor conversion efficiency owing to weak N₂ adsorption and the difficulty of N≡N triple bond dissociation. Herein, a Co single‐atom catalyst (SAC) model with a C‐defect‐evoked CoP₄ distorted configuration was fabricated using a selective phosphidation strategy, wherein P‐doping and C defects co‐regulate the local electronic structure of Co sites. Comprehensive experiments and theoretical calculations revealed that the distorted CoP₄ configuration caused a strong charge redistribution between the Co atoms and adjacent C atoms, minimizing their electronegativity difference. Consequently, the N₂ adsorption pattern switched from an “end‐on” to a “side‐on” mode with a high N₂ adsorption energy of −1.40 eV and an elongated N−N bond length of 1.20 Å, notably decreasing the N₂ adsorption/activation energy barrier. In the absence of sacrificial agents, the Co SAC achieved excellent photocatalytic overall N₂ fixation performance via an enzymatic pathway. The NH₃ yielding rate peaked at 1249.5 μmol h⁻¹ g⁻¹ with an apparent quantum yield of 3.51 % at 365 nm. Moreover, the selective phosphidation strategy has universality for synthesizing other SACs, such as those containing Ni and Fe. This study offers new insight into co‐regulating the electronic structure of SACs for efficient photocatalytic overall N₂ fixation.

Photocatalytic nitrogen (N₂) fixation over semiconductors has always suffered from poor conversion efficiency owing to weak N₂ adsorption and the difficulty of N≡N triple bond dissociation. Herein, a Co single‐atom catalyst (SAC) model with a C‐defect‐evoked CoP₄ distorted configuration was fabricated using a selective phosphidation strategy, wherein P‐doping and C defects co‐regulate the local electronic structure of Co sites. Comprehensive experiments and theoretical calculations revealed that the distorted CoP₄ configuration caused a strong charge redistribution between the Co atoms and adjacent C atoms, minimizing their electronegativity difference. Consequently, the N₂ adsorption pattern switched from an “end‐on” to a “side‐on” mode with a high N₂ adsorption energy of −1.40 eV and an elongated N−N bond length of 1.20 Å, notably decreasing the N₂ adsorption/activation energy barrier. In the absence of sacrificial agents, the Co SAC achieved excellent photocatalytic overall N₂ fixation performance via an enzymatic pathway. The NH₃ yielding rate peaked at 1249.5 μmol h⁻¹ g⁻¹ with an apparent quantum yield of 3.51 % at 365 nm. Moreover, the selective phosphidation strategy has universality for synthesizing other SACs, such as those containing Ni and Fe. This study offers new insight into co‐regulating the electronic structure of SACs for efficient photocatalytic overall N₂ fixation.

The electrochemical N₂ reduction reaction (NRR) currently represents a green and sustainable approach to ammonia production. However, the further progress of NRR is significantly hampered by poor catalytic activity and selectivity, necessitating the development of efficient and stable electrocatalysts. Herein, a nanoporous Fe–Mo bimetallic nitride (Fe₃N‐MoN) is synthesized using a molten‐salt preparation method. This catalyst demonstrates notable NRR performance, achieving a high NH₃ yield rate of 45.1 µg h⁻¹ mg⁻¹ and a Faradaic efficiency (FE) of 26.5% at −0.2 V (vs RHE) under ambient conditions. Detailed experimental studies and density functional theory (DFT) calculations reveal that the fabricated interface between Fe₃N and MoN effectively modulates the surface electronic structure of the catalyst. The interface induces an increase in the degree of electron deficiency at the nitrogen‐vacancy sites on the catalyst surface, allowing N₂ molecules to occupy the nitrogen vacancies more easily, thereby promoting N₂ adsorption/activation during the NRR process. Consequently, the Fe₃N‐MoN catalyst exhibits outstanding NRR activity. The insights gained from fabricating the Fe₃N‐MoN interface in this work pave the way for further development of interfacial engineering to prepare high‐efficient electrocatalyst.

Optimizing the local electronic structure of a single-atom catalyst (SAC) is crucial for efficient photocatalytic hydrogen evolution reactions. This study synthesized a Co-P₄/g-C₃N₄ heterostructure by selective phosphidation of the Co metal-organic framework/graphitic carbon nitride (Co-MOF/g-C₃N₄), converting the Co-O₆ configuration into a highly electronegative, coordinatively unsaturated Co-P₄ configuration anchored to a carbon matrix. P-doping induces strong charge redistribution, shifting the d-band center toward the Fermi level, transforming the Co sites from an electron-deficient state to an electron-rich state, and resulting in a significant reduction in the free energy barrier for HER to -0.08 eV. The Co-P₄/g-C₃N₄ heterostructure demonstrated a HER rate of 13.51 mmol g^-1 h^-1, approximately 4.82-8.35 times greater than those of photocatalysts loaded with noble metals. The apparent quantum efficiency (AQE) was 28.45% at 380 nm. The synergistic effect of the low coordination number and high electronegativity metal sites significantly enhances the photocatalytic HER performance.