Sibo Wang

Less order, more possibility: low-coordination site engineering unlocks the hidden potential of imperfect surfaces, transforming CO ₂ electroreduction into a powerful engine for carbon-neutral fuels.

The rapid recombination of photogenerated excitons in conjugated polymers constitutes a primary bottleneck for visible-light-driven photocatalytic hydrogen production. This challenge stems from the strong Coulomb binding between electrons and holes within these organic materials, which severely limits charge separation and transport. To overcome this limitation, this work presents a molecular synergy strategy through expanded fused-ring units and cyano group integration. The enlarged conjugated skeleton functions as an excited-state charge reservoir, extending carrier lifetime by providing spatial charge storage. Concurrently, cyano-derived pathways enable directional electron transfer to active sites. This synergistic design effectively suppresses nonradiative recombination and optimizes intramolecular charge distribution. The optimized polymer, TTA-sp2-CN, exhibits enhanced intrinsic dipole moment and superior charge transport capability, achieving a high hydrogen evolution rate of 23.05 mmol g–1 h–1 under visible light (λ > 420 nm) and an apparent quantum efficiency of 15.4% at 450 nm─performance that ranks among the outstanding reported for organic polymer photocatalysts. These findings establish a paradigm integrating charge reservoir construction and electron transfer modulation for designing high-performance organic photocatalysts.

Electrochemical CO ₂ reduction to ethylene (C ₂ H ₄ ) is fundamentally hindered by sluggish C–C coupling kinetics and inadequate control over intermediate dynamics. Herein, we propose a synergistic structural and electronic engineering strategy by designing Cu ₂ O@Ag yolk‐shell nanostructures (Cu ₂ O@Ag YSNs) as efficient tandem electrocatalysts. The yolk‐shell architecture induces a spatial confinement effect that locally enriches *CO intermediates, whereas the precisely tailored Ag‐Cu ₂ O hetero‐interface reconfigures the local electronic structure, fundamentally lowering the C–C coupling energy barrier. Driven by this dual synergy, the Cu ₂ O@Ag YSNs deliver a peak C ₂ H ₄ Faradaic efficiency of 36.17% and a partial current density of −10.18 mA cm ⁻² , significantly outperforming their monometallic counterparts and conventional Cu–Ag composites in both selectivity and durability. Ultimately, this work elucidates the critical role of spatial‐electronic coupling in tandem catalysis, providing a rational design strategy for regulating intermediate dynamics in CO ₂ electroreduction.

Solar‐driven direct propane dehydrogenation (PDH) represents a promising strategy to overcome the high‐temperature demands and selectivity limitations of conventional thermocatalysis, yet the identification of effective photoactive phases remains challenging. Herein, we demonstrate that photoactivated PtO ₂ enables regenerable and highly selective PDH over a PtO ₂ /Pt ₁ ‐In ₂ O ₃ catalyst under mild conditions. Under simulated sunlight without external heating, the catalyst achieves a propylene formation rate of 1322.35 µmol g ⁻¹ h ⁻¹ with unity selectivity, while remaining inactive under comparable thermocatalytic conditions. In situ spectroscopic analyses combined with density functional theory calculations reveal a photoactivated dual‐site mechanism, in which PtO ₂ nanoparticles function as oxidation centers for hole‐driven C─H bond activation, whereas neighboring interfacial Pt single atoms act as electron‐accepting sites to promote H ₂ evolution, enabling efficient spatial separation and utilization of photogenerated charge carriers. Catalyst deactivation arises from partial reduction of PtO ₂ , which can be exactly regenerated via a facile oxidative annealing process in air, affording excellent reusability. These findings identify photoactivated PtO ₂ as a distinct active phase for selective PDH and provide a design principle for solar‐driven alkane valorization.

Solar‐driven direct propane dehydrogenation (PDH) represents a promising strategy to overcome the high‐temperature demands and selectivity limitations of conventional thermocatalysis, yet the identification of effective photoactive phases remains challenging. Herein, we demonstrate that photoactivated PtO ₂ enables regenerable and highly selective PDH over a PtO ₂ /Pt ₁ ‐In ₂ O ₃ catalyst under mild conditions. Under simulated sunlight without external heating, the catalyst achieves a propylene formation rate of 1322.35 µmol g ⁻¹ h ⁻¹ with unity selectivity, while remaining inactive under comparable thermocatalytic conditions. In situ spectroscopic analyses combined with density functional theory calculations reveal a photoactivated dual‐site mechanism, in which PtO ₂ nanoparticles function as oxidation centers for hole‐driven C─H bond activation, whereas neighboring interfacial Pt single atoms act as electron‐accepting sites to promote H ₂ evolution, enabling efficient spatial separation and utilization of photogenerated charge carriers. Catalyst deactivation arises from partial reduction of PtO ₂ , which can be exactly regenerated via a facile oxidative annealing process in air, affording excellent reusability. These findings identify photoactivated PtO ₂ as a distinct active phase for selective PDH and provide a design principle for solar‐driven alkane valorization.

Defect engineering and electronic structure modification are central to the development of efficient metal oxide photocatalysts for overall water splitting. However, the role of specific electronic trap states that govern charge carrier dynamics remains incompletely understood. Herein, we report a lanthanide‐assisted solid‐state strategy to synthesize Sm ³⁺ ‐doped CeO ₂ that selectively suppresses detrimental Ce ³⁺ 4f ¹ trap states while preserving surface active sites. Structural and spectroscopic characterizations indicate that Sm ³⁺ preferentially segregates at the CeO ₂ surface, where its incorporation suppresses Ce ³⁺ 4f ¹ trap states that act as dominant non‐radiative recombination centers, thereby prolonging charge carrier lifetimes and enabling efficient migration to the catalytic surface. When integrated with dual cocatalysts (CoO _x –Rh/Cr ₂ O ₃ ), the optimized Sm ³⁺ ‐doped CeO ₂ achieves an apparent quantum yield of 12.6% ± 0.4% at 365 nm, representing the highest reported value for CeO ₂ ‐based photocatalysts for overall water splitting. These findings establish surface lanthanide segregation as a versatile approach for regulating defect states and charge carrier dynamics, unlocking the intrinsic activity of CeO ₂ for solar‐fuel production.

Defect engineering and electronic structure modification are central to the development of efficient metal oxide photocatalysts for overall water splitting. However, the role of specific electronic trap states that govern charge carrier dynamics remains incompletely understood. Herein, we report a lanthanide‐assisted solid‐state strategy to synthesize Sm ³⁺ ‐doped CeO ₂ that selectively suppresses detrimental Ce ³⁺ 4f ¹ trap states while preserving surface active sites. Structural and spectroscopic characterizations indicate that Sm ³⁺ preferentially segregates at the CeO ₂ surface, where its incorporation suppresses Ce ³⁺ 4f ¹ trap states that act as dominant non‐radiative recombination centers, thereby prolonging charge carrier lifetimes and enabling efficient migration to the catalytic surface. When integrated with dual cocatalysts (CoO _x –Rh/Cr ₂ O ₃ ), the optimized Sm ³⁺ ‐doped CeO ₂ achieves an apparent quantum yield of 12.6% ± 0.4% at 365 nm, representing the highest reported value for CeO ₂ ‐based photocatalysts for overall water splitting. These findings establish surface lanthanide segregation as a versatile approach for regulating defect states and charge carrier dynamics, unlocking the intrinsic activity of CeO ₂ for solar‐fuel production.

Constructing heterojunctions with built‐in electric fields (BIEFs) has emerged as an effective strategy to enhance charge separation in photocatalytic CO ₂ reduction. However, the photocatalytic activity and C ₂₊ selectivity of current copper oxide‐based heterojunctions remain insufficient for practical applications, largely due to inefficient interfacial charge transport and limited C─C coupling efficiency. Herein, we report a 0D/1D CuO _x /ZnO‐A400 photocatalyst featuring dual‐coherent Cu ₂ O/CuO/ZnO heterointerfaces with cascade built‐in electric fields to realize a photocatalytic C ₂ H ₄ evolution rate of 12.7 µ mol h ⁻¹ (5 mg of catalyst) with a selectivity of 44.1%. Advanced electron microscopy combined with density functional theory calculations reveals the formation of atomically coherent Cu ₂ O/CuO and CuO/ZnO interfaces. The directionally aligned BIEFs across the interfaces, pointing from Cu ₂ O to CuO and from CuO to ZnO, establish a cascade charge‐transfer pathway that accelerates the separation and migration of photogenerated carriers, thereby promoting the C─C coupling of CO ₂ molecules. This work provides an effective strategy for atomic‐scale interface engineering in multicomponent heterojunctions and offers new insights into the design of efficient photocatalytic systems for selective CO ₂ conversion into value‐added multicarbon products.

Among the emerging polymeric photocatalysts, poly(triazine imide) (PTI) has gained significant attention due to its highly crystalline framework, well‐defined electronic structure, and exceptional charge‐transport properties. These unique features position PTI as an attractive platform for exploring structure–property–performance relationships in photoredox catalysis. This review summarizes recent advancements in PTI‐based photocatalysts, with a particular focus on their enhanced performance in overall water splitting (OWS) and other applications. We analyze the fundamental structural and electronic characteristics that underpin photocatalytic activity. Furthermore, we discuss innovative synthetic methodologies and structural engineering strategies—including crystallinity control, electronic structure modulation, cocatalyst incorporation, and heterojunction design—aimed at optimizing charge separation, surface reaction kinetics, and active‐site utilization. Recent progress in PTI‐driven OWS, CO ₂ reduction, and other relevant processes is critically evaluated, along with the key challenges that impede efficiency and scalability. By elucidating the correlations between structure and its photocatalytic functions, this review offers design principles for the development of next‐generation crystalline polymer photocatalysts, and provides valuable insights for advancing practical solar energy conversion technologies.

Efficient suppression of photogenerated charge recombination remains a central challenge in photocatalytic water splitting. Bi ₄ Ti ₃ O ₁₂ is a promising ferroelectric semiconductor for overall water splitting, yet its quantum efficiency is fundamentally constrained by weak polarization and sluggish carrier dynamics. Herein, we demonstrate that isovalent A‐site substitution provides an effective route to amplify the intrisinc polarization of Bi ₄ Ti ₃ O ₁₂ through lattice regularization. Specifically, Sm substitution suppresses localization disorder by attenuating the stereochemical activity of Bi ³⁺ lone pairs, thereby reducing excessive octahedral tilting and enabling more coherent dipole alignment. The resulting enhanced ferroelectric polarization field markedly facilitates charge separation and carrier migration. In addition, post‐synthetic acid treatment tailors the surface termination and suppresses the self‐corrosion typically associated with bismuth‐based photocatalysts. Upon cocatalyst loading, the optimized Bi ₄ Ti ₃ O ₁₂ ‐Sm photocatalyst achieves an efficient overall water splitting with an apparent quantum efficiency of 10.5% at 365 nm. This work establishes structural regularization as a viable design principle for enhancing ferroelectric polarization and advancing high‐performance photocatalytic systems.