Naixu Li

Photothermal-assisted photocatalysis, which couples localized thermal energy with photogenerated charge carriers to overcome thermodynamic and kinetic limitations, has emerged as an effective strategy for solar-driven CO2 reduction. Herein, nanoflower-like NiO/ZnO p–n heterojunction spheres were rationally constructed via a simple hydrothermal calcination method to achieve efficient concentrated photothermal-assisted CO2 reduction. The unique nanoflower morphology provides abundant interfacial contact between NiO and ZnO, while the formation of the p–n heterojunction establishes an internal electric field that suppresses electron-hole recombination. Under concentrated irradiation (4.31 W·cm−2), the photothermal coupling effect reduces the apparent activation energy and enables the NiO/ZnO photocatalyst to deliver CO and CH4 production rates of 51.78 and 15.96 μmol·g−1·h−1, which are 7.92 and 9.61 times higher, respectively, than those obtained under nonconcentrated illumination. Photoelectrochemical measurements and in situ DRIFTS further reveal that the built-in electric field facilitates directional charge transfer from ZnO to NiO, thereby promoting CO2 adsorption and activation. We demonstrate an efficient photothermal-coupling strategy to construct high-performance catalysts for artificial photosynthesis and solar-to-fuel conversion.

Nanoconfined photothermal catalysis enables tackling energy transition and carbon neutrality by constructing precise micro/nanoconfined spaces to boost photothermal efficiency and reaction selectivity. This review systematically examines the technology's core mechanisms, advanced material design strategies, and cutting‐edge applications in solar fuel synthesis. We first elucidate how unique spatiotemporal field effects within confined microenvironments significantly improve photothermal efficiency and product selectivity, centered on efficient photothermal conversion, precise control of mass transfer‐adsorption, optimized reaction pathways, and synergistic coupling of photo‐thermal‐mass multi‐field interactions. Second, we detail key engineering strategies for high‐performance catalysis: precise construction of confinement architectures, rational integration of efficient photothermal components, atomic‐scale engineering of catalytic sites, and multifunctional interface optimization. The technology demonstrates transformative potential in light‐driven hydrogen production, high‐value CO ₂ conversion, CH ₄ dry/wet reforming, and directional transformation of light alkanes. However, critical challenges persist: unclear multi‐physical‐field coupling mechanisms; insufficient precision in sub‐nanomaterial synthesis and long‐term stability; thermal management‐mass transfer mismatches; reaction kinetics‐mass transfer trade‐offs; difficulty controlling complex reaction networks; and absent scale‐up pathways. This review clarifies the fundamental nature of confined catalysis to guide the development of novel multifunctional materials, break stability limits, achieve cross‐scale process intensification and system integration, ultimately advancing industrial‐scale, efficient, highly selective solar fuel synthesis technologies.

Light-driven dissipative self-assembly has garnered substantial attention due to its precise spatiotemporal controllability. However, achieving synergistic integration of spatial manipulation fidelity, architectural programmability, and dynamic reconfigurability within a free-standing platform remains a formidable challenge. Herein, we report a light-driven hierarchical dissipative self-assembly paradigm with temporally programmable fluorochromism, achieved through molecular-engineered coordination of dynamic macrocyclic host-guest interactions within sustainable cellulose matrices. Protonated vinylpyridium-derived merocyanine is designed and synthesized to construct light-controlled differential binding architectures with cucurbiturils. This system demonstrates quantitatively reversible interconversion between spiropyran and merocyanine states through alternating photoactivation (475 nm) and thermal relaxation. Structural modulation of host-guest stoichiometry between 1:2 and 1:1 induces nanoscale morphological switching between spherical and cuboid assemblies, accompanied by time-resolved fluorescence chromism. Leveraging the inherent affinity between cucurbiturils and cellulose nanofibrils, we engineered light-fueled hierarchical architectures into freestanding cellulosic papers, exhibiting self-erasing transient photowriting and multilevel anti-counterfeiting functions. The non-covalent host-guest architecture and reprocessable cellulose matrix synergistically enable material recyclability. This spatiotemporally programmed dissipative self-assembly system pioneers sustainable cellulose platforms for adaptive optoelectronics and smart sensing.

CO₂-to-hydrocarbon fuel conversion via artificial photosynthesis is limited by catalyst poisoning under high O₂ partial pressures and sluggish C₂-product formation. Herein, Ru_0.6Cu₁(Cu⁰–Cu¹⁺)/CeO₂ catalysts with adaptive O₂ tolerance are prepared by O₂-mediated dynamic interfacial reconstruction. Single-atom Ru doping at Ce lattice sites creates a trigonal prismatic coordination configuration, enabling proton-coupled electron transfer and accelerating H₂O dissociation. Photothermal effect promotes O₂-driven self-assembly of Cu⁰–Cu¹⁺ charge-gradient interfaces within Ru/Cu alloy clusters, thereby optimizing the adsorption behavior of ^*CHOCO intermediates and restructuring the C–C coupling pathway. Interfacial charge cascade transfer and geometric site synergy thermodynamically shift the product selectivity from C₁ to C₂, as determined by operando spectroscopy and electronic structure analysis. Under concentrated solar irradiation, the catalyst produces 549 ± 20 μmol·g⁻¹ C₂H₄ with 74.3% selectivity and 0.5% solar-to-chemical energy conversion efficiency—25-fold higher than that in non-concentrated systems. Dynamic interfacial regulation facilitates precise carbon chain synthesis in complex reaction networks.

The reconfiguration of catalysts in situ will obviously affect their catalytic performance, while the evolution process and the mechanism of reaction process remain unclear. Herein, a series of ternary Ni/In ₂ O ₃ /ZrO ₂ catalysts is prepared by the two‐step method. In the reaction atmosphere (CO ₂ /H ₂ ), In ₂ O ₃ particles are highly dispersed on the carrier ZrO ₂ , and are partially reduced to form InO _x layers. Moreover, In ₂ O ₃ tends to migrate near Ni species, forming the NiInO _x complex structure decorated by InO _x layers. It is demonstrated that indium oxide serves as the main active site in the reverse water‐gas conversion reaction, and Ni species function as an auxiliary agent to generate the strong metal‐support interaction effect with indium oxide, facilitate the formation of the key intermediates HCOO* and CO*, and further enhance the CO yield. Ab initio molecular dynamics and density functional theory calculations confirm that the In ₂ O ₃ clusters have undergone dynamic structural reconstruction on the ZrO ₂ support driven by temperature, and In ₂ O ₃ serves as the preferential adsorption site for CO ₂ .