Xiaoqiang Cui

A major challenge in artificial photosynthesis for H2O2 production arises from rapid charge recombination and non-selective side reactions. Herein, we design a Pd-decorated amorphous ZnCdS (Pd/AZCS) photocatalyst. Amorphization promotes bulk charge separation, while Pd loading enhances interfacial transfer, synergistically improving H2O2 selectivity and yield. Theoretical calculations reveal that amorphization and Pd loading synergistically enhance the dipole moment and modulate the electronic structure, resulting in significantly improved O2 adsorption capability. Spectroscopic analyses further confirm enhanced charge carrier separation and the formation of key intermediates in the oxygen reduction reaction (ORR). Consequently, the optimized Pd/AZCS achieves an impressive H2O2 evolution rate of 120.6 μmol g–1 min–1 in pure water without any sacrificial agents, representing a nearly 13-fold enhancement over pristine ZnCdS (ZCS). This work provides a pivotal strategy for efficient and durable photocatalytic H2O2 synthesis, highlighting its substantial promise for industrial-scale renewable energy applications.

2D covalent organic frameworks (COFs) have emerged as promising functional materials for catalysis, adsorption, sensing, and energy storage. Their interfacial behavior and surface microenvironment play a decisive role in performance, yet these features are typically considered static or irreversible due to the lack of dynamic structure models. In this study, we report the construction of an ionic COF (iCOF), I‐4, designed through precise tuning of its skeleton and counterions, which uniquely exhibits reversable dynamic exfoliation and aggregation behavior in aqueous environments. This enables bidirectional control over particle size and phase states. Photocatalytic hydrogen evolution (PHE) studies reveal a strong correlation between solution concentration, particle size, and hydrogen production efficiency. Notably, I‐4 achieves a remarkable PHE rate of 190 mmol g ⁻¹ h ⁻¹ at 35°C. Moreover, the material can be fully precipitated and recovered from solution by simple iodide salt addition, enabling closed‐loop material recycling. Mechanistic analysis based on weak‐force interactions and soft‐hard acid‐base theory provides insight into the dynamic exfoliation process, highlighting the synergistic roles of counterion assembly and framework structure. These findings pave the way for the tailored synthesis of next‐generation dynamic COF materials with reversible interfacial adaptability, offering broad application potential in catalysis, ion transport, and molecular separation.

Artificial photosynthesis offers a sustainable route for hydrogen peroxide (H ₂ O ₂ ) production, yet its efficiency is fundamentally limited by the kinetic decoupling of proton‐coupled electron transfer (PCET) during oxygen reduction. Here, we demonstrate that hydrogen radicals (H•) enable an alternative kinetic pathway for H ₂ O ₂ formation by accelerating the conversion of *OOH intermediates. This mechanism is realized through dual redox site regulation in Cu and O co‐modified Zn ₃ In ₂ S ₆ (denoted as O/Cu‐ZIS). The introduction of Cu dopants increases hole density in the Zn─S layers, accelerating water oxidation kinetics and facilitating interfacial proton availability for oxygen reduction, while oxygen incorporation modulates the electronic structure of the In–S layer to promote electron transport, enhance O ₂ activation, and weaken the interaction between protons and S sites. Quenching experiments and electron paramagnetic resonance spectroscopy support the participation of H• in the conversion of *OOH intermediates, providing an additional kinetic channel beyond conventional PCET. Finally, O/Cu‐ZIS achieves a H ₂ O ₂ production rate of 167.1 µmol g ⁻¹ min ⁻¹ from pure H ₂ O and O ₂ , markedly exceeds most state‐of‐the‐art photocatalysts. This work establishes H• as active intermediates in photocatalytic H ₂ O ₂ evolution and provides a strategy for regulating PCET via dual redox site design.

Photoreforming and photoelectroreforming have emerged as promising strategies for the solar‐driven valorization of waste‐derived feedstocks, offering a sustainable route to fuels and commodity chemicals. Unlike conventional thermochemical and biological processes, these photocatalytic and photoelectrocatalytic approaches operate under mild conditions, leveraging solar energy to activate complex organic substrates. Recent advances in artificial photosynthesis, including catalyst design, reaction engineering, and interfacial charge dynamics, have shown promise in improving selectivity and efficiency, yet fundamental challenges remain. Precise control over reaction pathways and suppression of undesirable side reactions remain difficult due to complex charge transfer kinetics, competing surface reactions, and limited stability under operational conditions. Addressing these challenges requires rational catalyst design to optimize charge transport, modulation of redox environments to enhance selectivity, and development of reactor architectures that maximize photon utilization and mass transfer efficiency. This review critically examines the mechanistic principles governing photocatalytic and photoelectrocatalytic waste valorization and discusses the central catalytic challenges. Finally, key challenges in process integration and scale‐up are assessed, and future directions are outlined for practical implementation of photoreforming in circular carbon and hydrogen systems.

Integrating metal atomic clusters (ACs) with single atoms (SAs) offers an effective strategy for designing high-performance catalysts for the oxygen reduction reaction (ORR); however, the immense combinatorial space of SA/AC configurations poses a formidable challenge for rational catalyst screening. To address this issue, we developed an integrated workflow combining the density functional theory, machine learning, and experimental validation, enabling the rapid and accurate identification of promising candidates. By employing the adsorption free energy of the OH* intermediate as a descriptor, 156 distinct SA/AC catalysts were systematically screened, leading to the identification of a Ru-cluster-modified Ir−N4 catalyst exhibiting high ORR activity, with a theoretical overpotential as low as 0.21 V. Electronic structure analysis reveals that Ru cluster modification lowers the Ir d-band center, reduces spin moments, and decreases orbital occupancy at the Ir site, collectively weakening OH* adsorption and thereby enhancing ORR kinetics. Guided by these theoretical predictions, we synthesized this catalyst, and its good ORR performance was confirmed (E1/2 = 0.841 V and robust durability: 16 mV degradation in E1/2). This study demonstrates a rational theory–experiment-integrated framework for the efficient discovery of high-performance SA/AC catalysts, providing a generalizable strategy to guide the development of advanced catalysts for a wide range of electrochemical reactions.

Electrocatalytic urea synthesis from carbon dioxide and nitrate offers a sustainable alternative to traditional energy‐intensive industrial processes. However, its practical application is hindered by sluggish reaction kinetics and intrinsically low C‐N coupling efficiency. Herein, we report a Cu@Cu ₃ P heterostructure catalyst featuring Cu nanoparticles anchored on Cu ₃ P nanosheets. The Cu@Cu ₃ P catalyst achieves a superior urea Faradaic efficiency of 50.47% and a urea yield rate of 137.78 µg h ⁻¹ mg ⁻¹ . Combined experimental and theoretical studies reveal that the interfacial coupling between hybridized orbitals of Cu ₃ P and unhybridized orbitals of Cu plays a critical role in modulating the adsorption behaviors of CO ₂ and NO ₃ ⁻ , while simultaneously facilitating C‐N coupling. This synergistic orbital interaction effectively lowers the energy barrier for key intermediates, leading to significantly enhanced urea selectivity. This work highlights the importance of interfacial orbital engineering in heterostructure catalysts and provides new insights into the rational design of high‐performance systems for efficient electrocatalytic urea synthesis.