Lele Wang

Photocatalytic methanol reforming affords a sustainable route for the synergistic production of hydrogen and high‐value formaldehyde; however, the atomic‐scale orbital interactions that fundamentally govern interfacial charge transfer and substrate activation remain a critical challenge. Herein, we overcome this challenge by developing a gradient 5 s –3 p –6 p (Cd 5 s –S 3 p –Bi 6 p ) orbital coupling strategy via in situ epitaxial growth of Bi ₂ S ₃ on CdS (BS/CdS‐H). This orbital coupling is defined as the gradient hybridization of Cd 5 s , S 3 p , and Bi 6 p orbitals across the epitaxial interface, forming a continuous orbital network that creates a directional electron migration channel and tailors the Cd 5 s orbital occupancy. Consequently, it simultaneously promotes interfacial charge separation and modulates Cd 5 s –O 2 p hybridization, which primarily facilitates O–H dissociation and thereby modulates the kinetic barrier for the subsequent C–H bond cleavage toward HCHO formation. The BS/CdS‐H heterojunction delivers exceptional H ₂ and HCHO co‐production rates of 5111.7 and 4630.0 µmol g ⁻¹ , representing 47.2‐ and 72.8‐fold enhancements over pristine CdS. This work establishes atomic‐scale orbital coupling as a predictive design principle that transcends conventional band‐alignment paradigms, offering a versatile orbital‐engineering framework for rational development of high‐efficiency solar fuel co‐conversion systems.

Photocatalytic reduction of nitroaromatics to amines is an attractive sustainable alternative to conventional hydrogenation. However, the commonly proposed sequential reduction pathway, involving multiple nitrogen-containing intermediates, can suffer from competing reaction routes and limited control over intermediate conversion, compromising chemoselectivity. Here we construct a face-to-face S-scheme heterojunction by integrating two-dimensional MoS2 nanosheets with a Cu-NTCDA metal–organic framework (CNM) to regulate the reduction pathway. The interfacial electric field promotes charge separation and migration, while the porous MOF enhances substrate enrichment. The optimized CNM1/Mo1 photocatalyst achieves high conversion and excellent stability under 425 nm LED irradiation, with broad functional-group tolerance and negligible dehalogenation of C–X (X = F, Cl, Br, I) bonds. In situ FTIR spectroscopy reveals an indirect coupling pathway involving an azobenzene intermediate that directs amine formation. This work demonstrates the potential of interfacial engineering to control reaction pathways for selective photocatalytic nitroaromatic reduction.

Spatially separated redox site engineering for dual-channel hydrogen peroxide (H2O2) photosynthesis has emerged as a promising strategy for the sustainable production of liquid solar fuels through artificial photosynthesis. Herein, a core–shell heterojunction composed of resorcinol-p-phthalaldehyde (RP) resin and In2S3 nanosheets is constructed to enhance H2O2 formation. The introduction of oxidative and π-conjugated RP kinetically accelerates charge separation and increases the surface charge density of the In2S3 photocatalyst significantly. Thermodynamically, the high redox potential and spatially separated active sites of RP/IS expand the H2O2 generation pathway from a single ORR route to a dual-channel mechanism incorporating both the oxygen reduction reaction (ORR) and water oxidation reaction (WOR). DFT calculations reveal that the synergistic enhancement of O2 and H2O adsorption further facilitates efficient H2O2 production. Upon visible-light irradiation, the optimized RP/IS achieves an impressive H2O2 production rate of 4193 μmol·g–1·h–1 in pure water. This study presents an innovative approach for enhancing H2O2 generation through the modulation of reaction pathways.

Aniline is a critical chemical feedstock for dyes, pharmaceuticals, and polymers, but its synthesis via nitroarene hydrogenation demands harsh conditions, precious metal catalysts, and incurs a substantial environmental footprint. Solar‐driven catalysis offers a sustainable alternative, but suffer from limited efficiency. Photothermal catalysis simultaneously utilize photothermal energy and charge carriers to overcome the reaction kinetics barriers, and has become a promising strategy. Here, we show that an Fe‐aminoterephthalate MOF (NM‐101) enables photothermal catalytic aniline synthesis with exceptional efficiency by synergistically coupling thermal energy and charge carrier activation. Under sunlight irradiation, NM‐101 achieves an aniline production rate of 303.13 mmol·g ⁻¹ ·h ⁻¹ with 100% selectivity and a turnover frequency (TOF) of 226.2 h ⁻¹ , surpassing all reported nonnoble metal photo(thermal)catalysts. Mechanistic studies reveal a direct hydrodeoxygenation pathway for the aniline production. In this process, photons not only provide thermal energy to drive the reaction but also generate carriers to participate in the reaction and reduce the activation barrier. When immobilized on 3D Al ₂ O ₃ foam, NM‐101 operates for 180 h and produces 42.2 g of aniline with a turnover number of 8470. This synergistic thermal and carriers overcomes kinetic bottlenecks in photocatalytic aniline production, demonstrating the feasibility and scalability of chemical synthesis using solar energy.

The solar-driven direct conversion of methanol to ethylene glycol, formaldehyde and simultaneous H₂ generation is an appealing strategy for converting sunlight to chemical energy. However, the low efficiency and stability of the photocatalyst remain critical bottlenecks hindering the practical implementation of this reaction. Herein, we synthesized the Cu₃P quantum dots/Cu-doped ZnIn₂S₄ p-n junction for efficient methanol oxidation and synchronous H₂ generation. The highly dispersed Cu₃P quantum dots promote electron–hole separation and furnish abundant catalytic sites. Moreover, the constructed p-n junction with a tight interface boosts the electron transfer, avoiding the serious photocorrosion of ZnIn₂S₄. Benefiting from these synergistic effects, the 2Cu₃P/Cu_0.5ZIS composite exhibits the highest photocatalytic conversion efficiency of methanol, yielding H₂, formaldehyde, and ethylene glycol with 10.34 mmol·g⁻¹·h⁻¹, 10.35 mmol·g⁻¹·h⁻¹ and 8.84 mmol·g⁻¹·h⁻¹ yields, which are 3.01, 3.05 and 3.10 times those of pure ZnIn₂S₄, respectively. A series of characterizations including X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and UV-Vis diffuse reflectance spectroscopy are employed to analyze the structure, composition, and photoelectrochemical properties of the materials. This work demonstrates a novel catalyst design paradigm for the high-efficiency solar light-driven photocatalytic activation of methanol enabling the co-production of value-added C1/C2 oxygenates and clean H₂ fuel simultaneously.

Developing efficient strategies to overcome catalytic performance limitations is essential for advancing photocatalytic and piezocatalysis applications. Herein, we propose a strategy that enhances catalytic performance by inducing compressive lattice strain via oxygen doping, to modulate the p-band center. Our study reveals that oxygen incorporation into CdS induces lattice contraction, leading to an upshift of the sulfur p-band center and an increased electronic density of states near the Fermi level, thereby strengthening the adsorption of reaction intermediates. Experimentally, O-doped CdS exhibits a 5.2-fold improvement in photocatalytic hydrogen evolution and a 3.8-fold increase in photocatalytic degradation activity, along with a 4.3-fold enhancement in piezocatalytic degradation efficiency. This work offers a new pathway for the design of efficient and stable catalytic materials through strain engineering.

An S-scheme heterojunction composed of resorcinol-formaldehyde (RF) resin and MgIn ₂ S ₄ (RF/MIS) was constructed to minimize the exciton binding energy of RF by modulating charge transfer pathways.

Covalent organic frameworks (COFs) have shown promise as photocatalysts for chemical transformations. However, their dense micropores and poor pore connectivity hinder mass transport and charge separation/transfer, limiting their efficiency. Herein, we develop a one‐step self‐sacrificing template strategy to synthesize three‐dimensional ordered macroporous COFs (3DOM‐COFs). This approach uniquely integrates in situ Tp–Tta COF crystallization with synchronized degradation of polystyrene templates under solvothermal conditions. This method introduces unreported kinetic match between template decomposition and framework growth. Such a confined growth mechanism leads to structurally robust and highly ordered macroporosity without post‐processing. 3DOM architecture enables uniform dispersion of fine ZnCdS nanoparticles for the generation a 3DOM‐COF based S‐scheme heterojunction, which exhibits remarkable performance in the oxidation of benzylamine (BA) for simultaneous N‐benzylbenzaldimine production with 99% selectivity at a rate of 15.1 mmol g ⁻¹ h ⁻¹ and H ₂ generation with a rate of 17.8 mmol g ⁻¹ h ⁻¹ . The 3DOM architecture confers 50‐fold faster mass transport than bulk COFs, while the heterojunction facilitates directional charge separation and interface charge transfer. Density functional theory calculations confirm that the heterojunction optimizes reaction thermodynamics by lowering the potential energy barriers of BA activation. The work pioneers a template‐concurrent synthesis paradigm, resolving COFs' critical pore engineering challenges.