Industrial seawater electrolysis remains constrained in achieving both high catalytic activity and long-term durability, with key limitations including structural degradation and mechanical instability within catalyst layers. Here we show a self-adhesive high-entropy oxide sub-nanowire monolithic catalyst that overcomes both obstacles. The catalyst is synthesized under mild conditions and incorporates 14 metal elements into uniform ~1.2 nm sub-nanowires with strong intrinsic adhesion to conductive substrates, eliminating the need for external binders. It also features unconventional active sites that enable efficient and durable lattice oxygen activation while preserving structural integrity during prolonged operation. It exhibits overpotentials of 129 mV in 1 M KOH and 153 mV in 1 M KOH + seawater at 10 mA cm-2, and maintains continuous operation at 1,000 mA cm-2 for 4,700 h and 4,400 h, respectively. Integrated into an anion exchange membrane seawater electrolyser, it delivers 3,000 mA cm-2 at 1.70 V (80 °C) and operates continuously for over 3,819 h at 2,000 mA cm-2 under ambient conditions.

The inherent low polarity and weak intermolecular interactions of nonpolar media impose a fundamental thermodynamic constraint on gelation. Despite recent breakthroughs in designing highly stretchable and tough hydrogels, developing organogels that absorb nonpolar organic liquids with comparable mechanical performance has remained elusive. We report an ultra-stretchable and crack-resistant nonpolar organogel engineered through an inorganic nanowire-polymer hybrid network, overcoming the elasticity-strength trade-off. This hybrid network can absorb and gelate diverse nonpolar organic liquids at mass absorption ratios reaching over 35:1. The resultant organogels exhibit outstanding mechanical properties, including breaking elongation up to 1600

A highly efficient and energy-saving photothermal synergistic catalytic oxidation technology was developed to eliminate ethyl acetate (EA) and 1,2-dichloroethane (1,2-DCE) over MoOx-TiO2, derived by MIL-125(Ti), supported Ru catalysts (Ru/MoOx-TiO2). The introduction of MoOx enhanced the light absorption capacity, carrier separation capacity and redox capacity of the catalyst, thus significantly improving the photothermal synergistic catalytic performance, with Ru/MoOx-TiO2 exhibiting outstanding activity for EA and 1,2-DCE oxidation (T90% = 212 and 319 °C, respectively). Meanwhile, the abundant Brønsted acidic sites on Ru/MoOx-TiO2 were inclined to generate more HCl and CO2, and reduce the release of chlorine-containing byproducts than that over Ru/TiO2. The characterization results by the in situ XPS, in situ PL and in situ EPR exhibited that the improvement of the photothermal synergistic catalytic oxidation performance was attributed to the coupling effect between electron migration on the catalyst surface and active oxygen species during the photothermal synergistic catalytic reaction process. This work has provided a promising path for simultaneously enhancing the removal efficiency of multi-component VOCs and the selectivity of target products.

Realizing the dehydrogenation direct pathway of formic acid electrooxidation reaction (FAOR) via sequential dehydrogenation steps is crucial for direct formic acid proton exchange membrane fuel cells (DFAPEMFCs). Herein, a twodimensional porous Pt/Ag@Bi2Te3 electrocatalyst featuring a triple-phase heterointerface is prepared via a visible light-induced strategy. The heterointerface effect and metal-support effect endow the Pt active sites with local electron-rich properties, thereby facilitating attack on the H atom of H-COO-H to cleave the C-H and O-H bonds and realize the direct pathway. The Pt/Ag@Bi2Te3 demonstrates remarkable FAOR mass and specific activities of 10.7 A & centerdot;mgPt-1 and 45.46 mA & centerdot;cm-2, outperforming commercial Pt/C by factors of 21.8 and 11.4, respectively. In the practical DFAPEMFC device, the Pt/Ag@Bi2Te3 delivers a peak power density of 116.2 mW & centerdot;cm-2, indicating its application potential. Density functional theory calculations further confirm the electron-rich Pt active sites and higher energy efficiency for the complete dehydrogenation direct pathway. This study provides a new strategy for preparing highly efficient FAOR catalysts for actual DFAPEMFCs.

Therapy based on heat and reactive oxygen species (ROS) generation have attracted increasing attention, while the weak photothermal ability and low ROS production have severely limited the efficiency of the tumor treatment. Here, 2D ultrathin CuS-phosphomolybdic acid (PMA) nanosheets are synthesized at sub-nanoscale. Typically, the improved second near-infrared light (NIR-II) light absorption, small bandgap, fast hot carrier response, abundant oxygen vacancies, and the electron delocalization between closely connected PMA and CuS units in sub-nanoscale result in the notably enhanced NIR-II photothermal therapy (PTT) performance of CuS-PMA. The reversible redox of Mo active sites in PMA provides basis for glutathione (GSH) depletion while triggering chemodynamic therapy (CDT) in the tumor microenvironment (TME), and the heat produced by the PTT greatly promotes the CDT and GSH depletion, where CuS-PMA presents sevenfold more ROS generation and fourfold more GSH depletion under PTT. In addition, the ROS generation/GSH depletion can downregulate heat shock proteins, weakening the heat resistance of tumor cells and thereby amplifying the killing effect of PTT. Moreover, the combination of antiprogrammed death-ligand 1 (alpha PD-L1) with the treatment of CuS-PMA promote the immunotherapy, resulting in the suppression of untreated abscopal tumors.

Stabilizing metastable electron-rich metals with atomic dispersion is critical for boosting tumor microenvironment (TME)-responsive catalysis and sonodynamic therapy (SDT), yet remains challenging. Herein, a "reverse growth" strategy is employed to kinetically trap Pd atoms from bulk Pd nanoparticles (NPs) via sub-nano CoSexOy-POM assemblies, forming atomically dispersed metastable electron-rich Pd clusters (Ternary-Pd). Electron delocalization at the sub-nanoscale induces electron rearrangement in the entire sub-nanostructure, thus enabling the acquisition of a novel electronic structure. Interestingly, the Pd clusters exhibit a more negative valence relative to 0-valent Pd. Specifically, such low-valent Pd clusters in an atomically dispersed state potently augment TME-responsive catalytic reactions, exhibiting a 15-fold enhancement in hydroxyl radical (•OH) generation for catalytic therapy, alongside enhanced hydrogen peroxide (H2O2)-responsive oxygen (O2) evolution that mitigates tumor hypoxia. Furthermore, their uniquely enriched electron density at the Pd active sites facilitates electron-hole separation, thereby potentiating SDT efficacy and resulting in a sixfold increase in singlet oxygen (1O2) yield. Abundant and different reactive oxygen species (ROS) induce mitochondrial oxidative stress, activating the caspase-1/GSDMD-mediated pyroptosis pathway. Besides, the introduced selenium (Se) doping promotes robust systemic immune responses to inhibit the growth of tumor metastases after oxidative stress.

Iron-substituted polyoxometalate (Fe-POM) clusters are promising candidates for photoelectrocatalytic nitrogen reduction due to their photosensitive and electron-buffering capabilities. However, their catalytic performances are severely hindered by the intrinsic cluster configuration and dissolution-induced detachment on the electrode. Here, using Fe-POM as "superatom" building blocks, we prepared a series of one-dimensional (1D) subnanowires and two-dimensional (2D) subnanosheets driven by different cation ligands, where clusters are connected directly with a controllable arrangement. Three kinds of Keggin-type clusters can be employed as building blocks, indicating the generality of this synthetic strategy. 1D subnanowires exhibit extraordinary catalytic activity toward the photoelectrocatalytic nitrogen reduction reaction (PEC-NRR), with a high ammonia yield of 72.0 μg h-1 mg-1, representing a 4.47-fold enhancement over the discrete clusters. Experimental and theoretical evidence demonstrate that electron delocalization among Fe-POM assemblies results in narrower band gaps and enhanced light harvesting, which also lowers the energy barrier for the rate-determining step (*NNH formation). Different from the microenvironment design of active sites, the superstructural engineering may offer a versatile paradigm for the electronic structure modulation of catalysts.

High entropy oxides (HEOs), composed of at least five nearly equimolar principal atoms occupying a similar sublattice, demonstrate promising catalytic potential but limited activity. Low-dimensional HEOs, serving as the metastable phase, possess distinctive electronic structures and fully exposed active sites, which anticipate showcasing appealing performance; however, their synthesis remains challenging. Herein, through the incorporation of clusters for kinetic control, a library of single-phase high entropy oxides (HEOs) with single-unit-cell thickness was synthesized under mild conditions (373 K). By modulating the surface entropies, including vibrational, translational, and rotational entropy, the synthesized high entropy subnano-oxides can exhibit structures, such as subnano-wires, subnano-sheets, and spiral coils. Contributed by the fully exposed active sites and electron delocalization among two-dimensional (2D) layer, HEOs presented as subnano-sheets display enhanced catalytic activity for photocatalytic reduction of CO2 to CH4, achieving a yield (5777 +/- 230.21 mu molg-1h-1), which is 41 times higher than that of bulk HEO obtained from the high-temperature calcination synthetic route.

Precise regulation of the d-band center of palladium (Pd) for targeted electrocatalysis held tremendous scientific and technological potential, yet achieving this via rational structural design remained challenging. Herein, we present medium-entropy amorphous alloyed single-atom (MEAASA) Pd nanosheets (NSs), wherein the d-band center of Pd was delicately modulated to an optimal value via the synergistic effect of medium-entropy alloying, single-atom coordination, and oxyphilic Cr/Mo/W modification. The as-synthesized PdCrMoW MEAASA NSs exhibited exceptional mass activities of 2.15 and 15.19 A mg- 1 for the oxygen reduction reaction (ORR) and ethylene glycol oxidation reaction (EGOR), respectively, which were 15.4 and 4.4 times higher than those of commercial Pt/C. Experimental results suggested that the optimized d-band center not only balanced the adsorption and activation of key intermediates but also suppressed CO formation via a non-CO dominated pathway, enabling a 4 e- ORR process and a nearly complete 10 e- EGOR process with 91.5% C1 selectivity. In practical direct ethylene glycol fuel cells (DEGFCs), the PdCrMoW MEAASA NSs delivered a peak power density of 117 mW·cm- 2, markedly outperforming the state-of-the-art commercial Pt/C catalyst.

Single-walled nanotubes have attracted extensive research interest since their discovery due to their remarkable physical and chemical properties. Here, we synthesized the single-walled cluster nanotubes with an atomically precise structure by directly linking the largest building blocks, Preyssler-type polyoxometalate clusters (each comprising ∼150 atoms) with rare-earth metal ions. The atomically precise assembly process of the nanotube enabled the capture of key growth intermediates, thereby revealing a cluster-to-cluster assembly pathway and leading to the proposal of a wall-fusion growth mechanism. Owing to electron delocalization between the internal polyoxometalate clusters, the nanotube exhibits exceptional catalytic activity for the electrocatalytic reduction of phenol to cyclohexanone, achieving 92% selectivity and 64% Faradaic efficiency. This work elucidates the molecular-level growth mechanism of single-walled cluster nanotubes and links their directional assembly to superior electron transport and catalytic efficiency, providing a conceptual foundation for the rational design of high-performance nanotube catalysts.

The activation of C-H bonds is a fundamental process in various chemical reactions, while faces significant challenge under mild conditions due to the high bond energy and low polarity. An ultrathin (∼3 nm) amorphous oxygen-containing carbon layer inserted into Pt/TiO2 yields C-O-M (M = Pt and Ti) dual interfaces. The photothermocatalytic consumption rate of n-heptane over Pt/C/TiO2 at 140 ℃ is 8.8 and 61.8 times higher than that over Pt/TiO2 and Pt/C, respectively. Temperature-programmed desorption (TPD) and density functional theory (DFT) calculations reveal that the constructed C-O-M interfaces significantly enhance the adsorption of hydrocarbon reactant, and decrease the C-H bond scission energy barrier. The photothermal X-ray photoelectron spectroscopy (XPS), femtosecond transient absorption (fs-TA) and electron paramagnetic resonance (EPR) experiments demonstrate that the C-O-Ti interface accelerates the electron migration and transforms the adsorbed oxygen into the superoxide species, thus efficiently oxidizing the reactant. Furthermore, introduction of an amorphous carbon layer to Pt/Al2O3, Pt/CeO2, Ce/TiO2 or Cu/TiO2 remarkably enhances the photothermal catalytic performance for propane, pentane, octane, toluene or hexanal oxidation. The unique effect of C-O-M dual interfaces induced via the ultrathin amorphous carbon layer provides a guideline for designing catalysts with efficient C-H bond activation ability.

Abstract Adhesives are applied extensively in daily life, and due to performance failure of conventional polymer adhesives in underwater environments, there is an urgent demand for highly stable underwater adhesives to meet application requirements of stable adhesion in humid environments and rapid leak sealing. Herein, crosslinking network of aluminum oxo clusters sub-nanoparticles (CN ASNPs) is prepared on a large-scale through a facile stirring reaction at room-temperature and atmospheric pressure, showing good gelation properties in non-polar solvents. The organogel exhibits outstanding underwater adhesive performance, arising from synergy effect of hydration layer disruption, micro-nano mechanical interlocking, high polymerization degree and intermolecular forces. And through being modified with perfluorodecyltriethoxysilane (FDETS) and methyltrimethoxysilane (MTMS), the adhesive performance can be further improved based on enhanced hydrophobicity and cohesion. The CN ASNPs organogel adhesive is suitable for various substrates, and for steel, the underwater adhesive strength can achieve ~2.41 MPa. More importantly, this adhesive exhibits excellent stability, whether in tap water or saltwater, whether under changed temperature (25~90 ℃) or prolonged time (~180 days) conditions. And this adhesive won’t cause any damage to substrates or leave hard-to-remove residues after bonding. Overall, the CN ASNPs organogel adhesive has great potential for practical applications in underwater and humid environments.

ABSTRACT Constructing metal single‐atom‐mediated Z‐scheme charge transmission is a promising yet challenging avenue to realize efficient solar photocatalysis. Here, a single‐atom Cu‐bridged TiO 2 hetero‐phase assembly with opened cavities and Z‐scheme charge transmission is fabricated via the illumination‐assisted preparation recipe. When tested for gas–solid photocatalytic CO 2 conversion, our photocatalyst displays an extraordinary activity with CH 4 production rate reaching to 327.19 µmol·g −1 ·h −1 , roughly 15.6 and 122.1 times enhancement than Degussa P25 TiO 2 and TiO 2 (B), and it outperforms those of Cu nanoparticles, Pd single atoms, Pt nanoparticles, Pd nanoparticles, and Au nanoparticles‐loaded counterparts as well as most TiO 2 ‐based composites ever reported. Based on the experimental test and theoretical calculation results, Cu single atoms act as the mediator to enhance interfacial charge transfer, which changes the photo‐carrier transmission pathway from type‐II to Z‐scheme, accounting for the significant promotion of photocatalytic capability. The study results could propel the marked optimization of photocatalytic efficiency by steering Z‐scheme charge transport with a single‐atom mediator.

ABSTRACT Water‐mediated photothermal CO 2 reduction to CH 4 is promising for renewable energy storage and carbon neutrality, but its selectivity and efficiency are limited by sluggish water dissociation that serves as a critical proton source and the demanding eight‐electron transfer barrier of CH 4 formation. These issues lead to insufficient protons for *CO hydrogenation. Herein, we engineer subnanoscale CeO 2 ‐Cu 2 O heterostructured subnanowires with densely enriched CeO 2 ‐Cu 2 O interfaces to overcome this proton bottleneck. Experimental and theoretical simulation results demonstrate that these interfaces accelerate H 2 O dissociation and create a “proton‐rich microenvironment,” which boosts the proton supply rate to match the kinetic demand of *CO hydrogenation. This directs the protonation of *CO to *CHO instead of CO desorption; these intermediates then convert to *CH 2 O and *CH 3 O, achieving over 99% CH 4 selectivity and a record yield of 2818 μmol g −1 h −1 . This yield is 15‐fold higher than that of bulk and nanoparticle counterparts, underscoring the key role of subnanoscale interface enrichment in optimizing multielectron reactions.

Two-dimensional (2D) network structures with efficient carrier transport and surface reactivity provide powerful platforms for heterogeneous photocatalysis. Complexes containing 5f metals exhibit remarkable photo-reactivity but are limited by instability, unsustainability, and inefficient carrier dynamics. Here, we report UNbO clusterphene, the first subnanomaterial incorporating 5f metals, created by integrating uranyl ions with polyoxoniobate clusters into a 2D hexagonal structure. This visible-light-responsive catalyst shows excellent activity for oxidative alkene cleavage, enabling gram-scale reactions, recyclability, and compatibility with 28 alkenes. Mechanistic studies indicate a superoxide radical-mediated oxidation pathway. Meanwhile, calculations reveal that planar carrier migration within the clusterphene extends carrier lifetimes and suppresses electron-hole recombination, enhancing photocatalytic performance. This work demonstrates a robust and efficient uranyl-containing heterogeneous photocatalyst and represents the first integration of 5f metals with clusters at the subnanoscale, offering a broadly generalizable strategy for designing high-performance subnanocatalysts for photocatalysis.

Photoelectrochemical nitrogen (N) fixation to ammonia (NH3) is a sustainable route for hydrogen storage yet limited by the stubborn N≡N bond and competitive interfacial reaction kinetics. Inspired by nitrogenase, we design single-atom iron (Fe)-doped tungsten oxide (WO3) subnanowires as a bioinspired, dynamically integrated catalytic platform to systematically overcome these challenges: (i) The distorted lattice and asymmetric sites create a dynamically responsive catalytic center, where photoinduced valence-lattice oscillation drives electron delocalization, shifting the conventional N2 adsorption mode and reaction pathway; (ii) the unique self-adhesive and film-forming properties enable robust, binder-free electrodes with maximized active-site exposure; and (iii) surface ligand engineering establishes a bioinspired microenvironment that selectively enriches N2 and regulates proton access. This system achieves an NH3 yield of 286 micrograms per milligram of catalyst per hour, a 24-fold improvement over conventional Fe-WO3 nanowires, with stable performance over 30 cycles. This work demonstrates functionally integrated, bioinspired catalysis at the subnanoscale, offering a paradigm for efficient molecular conversion.

Atomically dispersed single-site catalysts (ADCs) have demonstrated exceptional catalytic performance that surpasses traditional catalysts, attributed to their higher atom utilization efficiency. However, a general engineering approach for converting metal-oxo clusters into efficient and stable ADCs has not been established. In this work, a universal conversion strategy is reported to synthesize a series of noble metal ADCs (NM@WO2-W, NM = Ir, Pt, Ru, and Pd) through the engineering of polyoxometalates (POMs), a well-established type of metal-oxo clusters. This strategy confines the single noble metal atom within the lattice of WO2, thereby creating lattice-confined ADCs. The as-prepared Pt@WO2-W exhibits enhanced catalytic activity for the hydrogen evolution reaction (HER), with an impressively low overpotential of 49 mV at 50 mA & centerdot;cm-2 and robust durability over 50 h, with only 0.2% current density decay. Furthermore, the catalytic behavior of NM@WO2-W in the oxygen evolution reaction (OER) has also been explored, highlighting the superior electrocatalytic activity and durability of Ir@WO2-W. In situ experiments and density functional theory calculations further reveal the intrinsic activity of NM@WO2-W for both HER and OER. This work introduces a general strategy for the rational design of lattice-confined ADCs through conversion of metal-oxo clusters, providing efficient and stable ADCs for water electrolysis.

Constructing metal single-atom-mediated Z-scheme charge transmission is a promising yet challenging avenue to realize efficient solar photocatalysis. Here, a single-atom Cu-bridged TiO2 hetero-phase assembly with opened cavities and Z-scheme charge transmission is fabricated via the illumination-assisted preparation recipe. When tested for gas-solid photocatalytic CO2 conversion, our photocatalyst displays an extraordinary activity with CH4 production rate reaching to 327.19 µmol·g-1·h-1, roughly 15.6 and 122.1 times enhancement than Degussa P25 TiO2 and TiO2(B), and it outperforms those of Cu nanoparticles, Pd single atoms, Pt nanoparticles, Pd nanoparticles, and Au nanoparticles-loaded counterparts as well as most TiO2-based composites ever reported. Based on the experimental test and theoretical calculation results, Cu single atoms act as the mediator to enhance interfacial charge transfer, which changes the photo-carrier transmission pathway from type-II to Z-scheme, accounting for the significant promotion of photocatalytic capability. The study results could propel the marked optimization of photocatalytic efficiency by steering Z-scheme charge transport with a single-atom mediator.

ABSTRACT Water‐mediated photothermal CO2 reduction to CH4 is promising for renewable energy storage and carbon neutrality, but its selectivity and efficiency are limited by sluggish water dissociation that serves as a critical proton source and the demanding eight‐electron transfer barrier of CH4 formation. These issues lead to insufficient protons for *CO hydrogenation. Herein, we engineer subnanoscale CeO2‐Cu2O heterostructured subnanowires with densely enriched CeO2‐Cu2O interfaces to overcome this proton bottleneck. Experimental and theoretical simulation results demonstrate that these interfaces accelerate H2O dissociation and create a “proton‐rich microenvironment,” which boosts the proton supply rate to match the kinetic demand of *CO hydrogenation. This directs the protonation of *CO to *CHO instead of CO desorption; these intermediates then convert to *CH2O and *CH3O, achieving over 99% CH4 selectivity and a record yield of 2818 μmol g−1 h−1. This yield is 15‐fold higher than that of bulk and nanoparticle counterparts, underscoring the key role of subnanoscale interface enrichment in optimizing multielectron reactions.

The landscape of nanocatalytic therapy and sonodynamic therapy (SDT) is confronted with formidable challenges, including the rapid consumption of nonrenewable Fenton-like nanocatalysts, inefficient carrier separation in sonosensitizers, and hypoxia in tumor microenvironment (TME). Herein, we develop high-entropy oxide (HEO)-phosphomolybdic acid (PMA) ultrathin nanoleaves in subnanoscale (SHPL), featuring periodic heterounit alternation of HEO nuclei and PMA clusters with obvious lattice tensile strain. Notably, the lattice tensile strain in this leaf structure reduces hydrogen peroxide (H2O2) dissociation/adsorption energies, promoting chemodynamic therapy (CDT)-mediated hydroxyl radical (•OH) generation and oxygen (O2) production to alleviate hypoxia for enhanced SDT. More importantly, the periodic HEO-PMA heterostructures serve as charge mediators, enabling efficient separation of ultrasound (US)-induced electron-holes to augment singlet oxygen (1O2) yield for SDT. Additionally, the well-engineered energy band structure enables excited electrons to flow smoothly to HEO units, rapidly converting FeIII to FeII as regenerated Fenton-like nanocatalysts and boosting CDT in the TME. As a result, the SHPL exhibits more than 30-fold reactive oxygen species (ROS) production in simulated TME. The enhanced nanocatalytic reactions and SDT fully activate immune response, achieving the suppression of tumor metastases.