Yuzhu Ma

Urea‐assisted water electrolysis represents a sustainable paradigm for concurrent hydrogen production and wastewater remediation; however, its efficiency is fundamentally limited by the Sabatier trade‐off between urea activation and CO ₂ product desorption. Here, we report an asymmetric electronic structure engineering strategy to overcome this bottleneck by incorporating atomically dispersed Ni into Co ₃ O ₄ cubic hollow nanoboxes. The construction of asymmetric Ni–O–Co sites triggers a critical spin‐state transition of octahedral Co ³⁺ from low‐spin to intermediate‐spin through lattice distortion and polarization. This electronic reconfiguration effectively strengthens urea binding while simultaneously weakening the adsorption of poisonous *CO ₂ intermediates. Synergized by a superhydrophilic and superaerophobic surface that facilitates rapid bubble release, the Ni _SAC ‐Co ₃ O ₄ catalyst achieves an exceptionally low potential of 1.32 V for urea oxidation. In a full‐cell configuration, the system delivers a current density of 10 mA·cm ⁻² at only 1.34 V, doubling the hydrogen output compared to traditional water splitting while achieving a 96.7% urea degradation efficiency. Life cycle assessment further validates the environmental superiority of this system. Our work provides a versatile design principle for tailoring spin states in asymmetric architectures to break linear scaling relationships in complex multi‐electron electrocatalysis.

Urea‐assisted water electrolysis represents a sustainable paradigm for concurrent hydrogen production and wastewater remediation; however, its efficiency is fundamentally limited by the Sabatier trade‐off between urea activation and CO ₂ product desorption. Here, we report an asymmetric electronic structure engineering strategy to overcome this bottleneck by incorporating atomically dispersed Ni into Co ₃ O ₄ cubic hollow nanoboxes. The construction of asymmetric Ni–O–Co sites triggers a critical spin‐state transition of octahedral Co ³⁺ from low‐spin to intermediate‐spin through lattice distortion and polarization. This electronic reconfiguration effectively strengthens urea binding while simultaneously weakening the adsorption of poisonous *CO ₂ intermediates. Synergized by a superhydrophilic and superaerophobic surface that facilitates rapid bubble release, the Ni _SAC ‐Co ₃ O ₄ catalyst achieves an exceptionally low potential of 1.32 V for urea oxidation. In a full‐cell configuration, the system delivers a current density of 10 mA·cm ⁻² at only 1.34 V, doubling the hydrogen output compared to traditional water splitting while achieving a 96.7% urea degradation efficiency. Life cycle assessment further validates the environmental superiority of this system. Our work provides a versatile design principle for tailoring spin states in asymmetric architectures to break linear scaling relationships in complex multi‐electron electrocatalysis.

Biomimetic multi-compartment nanoreactors (BMNRs) have emerged as a highly active and cutting-edge research direction in materials science and chemistry. Inspired by the multi-chamber structure and function of biological systems such as cells, the synergistic improvement of catalytic efficiency, catalytic selectivity, and drug delivery accuracy can be achieved by precisely regulating the number, scale, shape, and combination of chambers within the multi-chamber structure. This review first introduces strategies for preparing multi-compartment structures based on different substrates (including carbon, silicon, and metal compounds). Subsequently, the specific advantages of multi-chamber structures (including independent, isolated and interconnected multi-compartment structures) in catalysis, energy storage, and biomedical fields are discussed. Finally, the future opportunities of multi-chamber nanoreactors are outlined. This review emphasizes the advantages of emerging technologies, such as 3D printing, in adjusting multi-chamber structures and designs in nanotechnology and the development of nano-robots capable of autonomous navigation and performing complex tasks in vivo that can overcome the technical bottleneck of drug delivery.

Modulating the molecule adsorption-desorption behaviors of solid catalysts is important for fulfilling complicated catalytic purposes. Herein, we quantitatively reveal the dynamic balancing of molecule adsorption/desorption by curvature modulation on a series of self-pressurizing mesoporous nanoreactors with controlled concave-convex Gaussian curvatures via a programmable nanodroplet buckling strategy. The encapsulation of Fe₃O₄ nanoparticles in the cavity produces a large temperature difference between the nanoreactor surface (193.8 °C) and the reaction medium (73.7 °C) under photoexcitation, forming thermally confined self-pressurizing nanoreactors. Together with the external pressure exerted by the liquid-surface-tension on the concave-convex surfaces, the self-pressurizing drives the dynamic regulation of molecule adsorption-desorption on the Gaussian surface. Based on this, the nanoreactor with catalytic metallic Ru on the outer shells achieves the high-selective cascade oxidation of biomass-derived 5-hydroxymethylfurfural to high-value-added 5-formyl-2-furancarboxylic acid (97.9% selectivity), showing a reaction efficiency that is an order of magnitude higher than that of conventional heating.

Constructing advanced semiconductor nanoreactors is an effective route to boost the efficient photocatalytic conversion of biomasses to high‐value‐added products. Herein, single‐atom anchored flower‐like mesoporous TiO₂ nanoreactors with tunable anatase‐rutile crystalline phases are prepared via a micelle‐interface confined co‐assembly strategy (Ru_0.5/A&R‐TNs). This approach not only facilitates the introduction of various monatomic/diatomic (e.g., Ru, Mo, Pd, Pt, etc.) sites but also spontaneously induces the TiO₂ phase transformation from anatase to rutile, achieving precise control of two‐phase ratios. The interface of the two phases with abundant oxygen vacancies (O_v) facilitates the adsorption and activation of 5‐hydroxymethylfurfural (HMF), which exhibits a high photocatalytic HMF oxidation to DFF (selectivity of 90.8%). Based on the optimal phase compositions, the doping of Ru single‐atom further exhibits a high atom utilization and suitable electronic structure. Therefore, the Ru_0.5/A&R‐TNs achieve the cascade conversion from HMF to 5‐formyl‐2‐furoic acid with a selectivity of 75.8%. This research provides innovative ways for single‐atom catalyst synthesis, and the mechanism of synergistic catalytic action may provide new guidance for the photocatalytic conversion of high‐value‐added products from HMF.

Developing artificial nanomaterial systems that can convert external stimuli to achieve nanoscale self-sustainable motion (for example, self-rotation), and simultaneously integrate and deploy the spatial localization of multiple active sites to unravel the intraparticle diffusion patterns of molecules, is of great importance for green synthetic chemistry. Here we show a paddle-like self-stirring mesoporous silica nanoreactor system with separated chambers and controllable proximity of active sites. The nanoreactors are designed by encapsulating magnetic Fe₃O₄ (~20 nm) in the first chamber, and meantime, Au and Pd nanocrystals are spatially isolated in different domains. Such a nanoreactor generates nanoscale rotation under the rotating magnetic fields and exhibits an order of magnitude activity enhancement in the cascade synthesis of 5,6-dimethylphenanthridinium (96.4% selectivity) compared with conventional macro-stirring. Meanwhile, we quantitatively uncovered the rotation-induced enhancement in sequential and reverse transfer of reactive intermediates, consequently revealing the relevance of self-rotation and proximity effects in controlling the catalytic performance.

Crystal‐facet heterojunction engineering of mesoporous nanoreactors with highly redox‐active represents an efficacious strategy for the transformation of CO₂ into valuable C₂ products (e.g., C₂H₄). Herein, hollow mesoporous cube‐like CuS nanoreactors (~860 nm) with controlled anisotropic crystal‐facets are prepared through an interfacial‐confined ion dynamic migration‐rearrangement strategy. The regulation of the S²⁻ ion concentration facilitates the modulation of the highly active (110) to (100) crystal‐facet ratios from 0.119 to 0.288, and induces the formation of anisotropic crystal‐facet heterojunctions. The controllable crystal‐facet heterojunctions trigger the directional charge carrier migration, and are accompanied with the formation of tandem S‐defect sites (Cu₀‐S₁@S₃). Both of them promote the efficient electron‐hole pair dissociation and attain asymmetric C−C coupling. The hollow mesoporous CuS nanoreactors with optimized crystal‐facet ratio of 0.224 (HMe‐CuS‐3) deliver a high selectivity of 72.7 % for the photocatalytic reduction of CO₂ to acetylene (C₂H₂). Further constructed Au‐(110) and Co₃O₄‐(100) spatially separated cascade nanoreactors (SS‐Au@Co₃O₄‐CuS) achieve CO₂‐C₂H₄ photoreduction, in which the Co‐sites enhance H₂O dissociation to provide protons and the protonation of *CO to *COH. The *COH is further captured by Au‐sites to accomplish the asymmetric *CO‐*COH coupling and subsequent protonation, ensuring a high C₂H₄ generation rate of 4.11 μmol/g/h with a selectivity as high as 90.6 %.

Crystal‐facet heterojunction engineering of mesoporous nanoreactors with highly redox‐active represents an efficacious strategy for the transformation of CO₂ into valuable C₂ products (e.g., C₂H₄). Herein, hollow mesoporous cube‐like CuS nanoreactors (~860 nm) with controlled anisotropic crystal‐facets are prepared through an interfacial‐confined ion dynamic migration‐rearrangement strategy. The regulation of the S²⁻ ion concentration facilitates the modulation of the highly active (110) to (100) crystal‐facet ratios from 0.119 to 0.288, and induces the formation of anisotropic crystal‐facet heterojunctions. The controllable crystal‐facet heterojunctions trigger the directional charge carrier migration, and are accompanied with the formation of tandem S‐defect sites (Cu₀‐S₁@S₃). Both of them promote the efficient electron‐hole pair dissociation and attain asymmetric C−C coupling. The hollow mesoporous CuS nanoreactors with optimized crystal‐facet ratio of 0.224 (HMe‐CuS‐3) deliver a high selectivity of 72.7 % for the photocatalytic reduction of CO₂ to acetylene (C₂H₂). Further constructed Au‐(110) and Co₃O₄‐(100) spatially separated cascade nanoreactors (SS‐Au@Co₃O₄‐CuS) achieve CO₂‐C₂H₄ photoreduction, in which the Co‐sites enhance H₂O dissociation to provide protons and the protonation of *CO to *COH. The *COH is further captured by Au‐sites to accomplish the asymmetric *CO‐*COH coupling and subsequent protonation, ensuring a high C₂H₄ generation rate of 4.11 μmol/g/h with a selectivity as high as 90.6 %.

Porous nanoreactors mimic the structures and functions of cells, providing an adaptable material with multiple functions and effects. These reactors can be nanoscale containers and shuttles or catalytic centres, drawing in reactants for cascading reactions with multishelled designs. The detailed construction of multi-level reactors at the nanometre scale remains a great challenge, but to regulate the reaction pathways within a reactor, designs of great intricacy are required. In this Review, we define the basic structural characteristics of porous nanoreactors, while also discussing the design principles and synthetic chemistry of these structures with respect to their emerging applications in energy storage and heterogeneous catalysis. Finally, we describe the difficulties of the structural optimization of these reactors and propose possible ways to improve porous nanoreactor design for future applications.