The direct synthesis of methanol via CO2 hydrogenation represents a promising technology for CO2 mitigation and utilization. However, achieving high catalytic activity and selectivity remains challenging due to kinetic and thermodynamic constraints. Herein, we report a series of hydrotalcite-derived CuZnAl nanocatalysts featuring highly dispersed Cu species with tunable electronic and geometric structures, achieved by precisely controlling copper content and structural topological transformation processes. The hydrotalcite-derived CuZnAl catalyst demonstrates an exceptional normalized CO2 reaction rate of 535.46 mmol.g(Cu)(-1).h(-1) and 79% methanol selectivity, yielding an excellent methanol space-time yield (similar to 13.60 g.g(Cu)(-1).h(-1)) under mild conditions (240 degrees C, 3 MPa). This is approximately twice that of conventional Cu/ZnO/Al2O3 catalyst and ranks among the highest reported for Cu-based systems. Operando CO2 FTIR and structure-activity analysis reveal that the interfacial Cu species serve as intrinsic active centers, altering the rate-determining step and reaction pathway. Specifically, this modification favors CO2 hydrogenation via key HCOO* intermediates, which exhibits a lower activation energy compared to the traditional CO* pathway observed on conventional Cu/ZnO/Al2O3 catalyst. This accounts for the superior catalytic performance for CO2 hydrogenation to methanol. This work advances the structural design and controllable synthesis of efficient Cu-based catalysts for high-value utilization of carbon resources.

Oxidative propane dehydrogenation (OPDH) has emerged as a promising approach for direct propylene production. However, it still confronts great challenge of overoxidation of propane to COx, damaging the products selectivity. Herein, we report an electrically-driven continuous chemical looping process to efficiently produce propylene via an electrochemical CO2-OPDH system within solid oxide electrolysis cells (SOECs). At an optimal current density of 10 mA cm-2, the system with a Co3O4-modified La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) anode achieves 92.6% olefin selectivity and 14.2% single-pass propane conversion. This current-driven configuration boosts the propylene yield (5.11 mmol gtotal-1 h-1) by a factor of 18.5 over the open-circuit baseline. The electrochemical CO2-ODHP system also exhibits good stability during a 120-hour durability test. In-situ characterization and theoretical calculations elucidate the electrically driven online replenishment mechanism of Co3O4 lattice oxygen by O2- derived from cathode CO2 reduction. This dynamic cycle maintains moderate anode surface oxygen activity, resulting in highly efficient and selective OPDH without significant over-oxidation or cracking of propane.

Importing oxygen vacancies into semiconductor titanium dioxide can effectively modulate its electronic structure, enhancing visible light absorption and photocatalytic performance. In this study, a novel nitrogen-doped Ti3CNTx MXene precursor was transformed into an amino-modified, oxygen-deficient TiO2/C nanosheet composite using a unique and efficient ionizing radiation oxidation method. The resulting oxidation-derived material, designated as RO-Ti3CN, was utilized for the visible light photocatalytic reduction of Cr(VI) pollutants. The presence of oxygen vacancies and carbon broadens the absorption range of visible light, promoting the separation of photogenerated electrons and holes. By modulating the morphology, the specific surface area of RO-Ti3CN was increased, and the amino groups on the material surface facilitated the interaction with Cr(VI). The apparent rate constant for the photocatalytic reduction of Cr(VI) using the synthesized material was found to be 0.015 min-1, which is 11.5 times higher than that of the commercial catalyst P25 under the same conditions. This study successfully demonstrated the efficient derivation of Ti3CNTx MXene and highlighted the superiority of the room temperature radiation oxidation method in producing high-performance photocatalysts.

Ammonia (NH3) synthesis is among the greatest discoveries in human history. While dinitrogen (N2) is converted in nature under ambient conditions to NH3 through an associative mechanism at the FeMoco active site of nitrogenase, the industrialized Haber-Bosch process involves an N2 dissociative mechanism on the C7 site of iron or the B5 site of ruthenium, which requires harsh conditions of high temperatures (430-500 °C) and high pressures (10-30 MPa). Here, we report a new active site of Ru1Mo6 bimetallic single-cluster anchored on Mo2CTx MXene for efficient NH3 synthesis. This highly stable catalyst can achieve N2-to-NH3 thermal synthesis under mild conditions (T = 50 °C and P = 0.1 MPa). An exceptionally high NH3 production rate of 3230 mmol gRu-1 h-1 with >1000 h of long-term stability has been achieved at 400 °C and 1 MPa, which is roughly three times higher than those of highly dispersed Ru catalysts ever reported. This new catalyst featuring an atomically precise single-cluster active site holds promise for designing robust catalytic systems for N2-to-NH3 thermal conversion under mild conditions.

ABSTRACT Methanol aqueous reforming reaction (APRM) provides a green and clean route towards hydrogen production, in which the structure design and preparation of efficient catalysts remains a challenge. Herein, we report a platinum catalyst supported on the porous hydroxyl lanthanum oxide, which is prepared via glycine combustion method followed by a reduction process. The optimized 0.8%Pt/La catalyst, which is featured by Pt single‐atom dispersed on a La 2 (OH) 2 x O 3‐2 x support, exhibits an extraordinary catalytic performance towards APRM. A H 2 production rate of 7672 µmol H2 g cat −1 min −1 and an average turnover frequency (ATOF) of 11973 h ‒1 are obtained, which is preponderant to the state‐of‐the‐art catalysts. An in‐depth investigation based on kinetic isotope analysis, in situ spectroscopy characterizations and theoretical calculations substantiates that Pt single atom coordinated with adjacent lattice hydroxyl (OH L ) with electron transfer from Pt to support serves as the intrinsic active site, in which the Pt δ + site promotes the dehydrogenation of methoxyl whilst lattice hydroxyl directly participates in the oxidative coupling process (CH 2 O* + OH L → CH 2 OOH*). Furthermore, the Pt δ + −(OH L ) x −La interface sites can remarkably reduce the energy barrier of CH 2 OOH* dehydrogenation (rate‐determining step), and the resulting hydroxyl vacancies can boost H 2 O dissociation to recover consumed OH L , accounting for the exceptional catalytic performance.

ABSTRACT Single metal‐coordinated nitrogen‐doped carbon (M 1 ‐NC) materials hold great promise for electrocatalytic CO 2 reduction, yet the precise modulation of their nitrogen configurations to steer ethanol selectivity remains a formidable challenge. Here, we designed Cu 1 ‐NC anchored on a carbon support featured with a high pyrrolic‐N to pyridinic‐N ratio (CuN 4 /pr‐h‐NC), which enables an exceptional Faradaic efficiency (FE) of 79.6% for ethanol. Experimental and theoretical studies reveal that pyrrolic‐N and pyridinic‐N synergize with Cu sites to form novel triadic sites, which regulate the potential‐determining step (PDS) from the traditional C–C coupling step to the protonation step of *CO to *COH. Pyrrolic N boosts *CO surface coverage, after which *CO migrates to neighboring pyridinic N sites for hydrogenation to *COH. The resulting *COH readily couples with another *CO at the single Cu site, driving selective ethanol formation. Due to the single‐metal‐surface‐independence of PDS, this mechanism extends to metals traditionally considered inactive for C–C coupling (M = Fe, Co, Ni, Zn). A positive correlation is observed between the ethanol FE and the pyrrolic N/pyridinic N ratio across the series, with ZnN 4 /pr‐h‐NC reaching 71.8% at –0.5 V versus RHE. This work establishes an ensemble site engineering strategy to rationally steer CO 2 to ethanol pathways for M 1 ‐NC electrocatalysts.

Proton exchange membrane water electrolysis (PEMWE) requires highly active and durable acidic oxygen evolution reaction (OER) anodes, yet the benchmark IrO2 is limited by its scarcity and high cost. RuO2 is a more cost-effective and active alternative, but suffers from poor acidic stability due to lattice oxygen instability and Ru over-oxidation under anodic conditions. Here we incorporate larger Zr4+ (4 d0) into rutile RuO2 to form Ru1-xZrxO2 solid-solution nanosheets. Diffraction and spectroscopic analyses reveal that Zr4+ incorporation into the RuO2 lattice induces long-range lattice expansion, elongates Ru-O bonds, and thereby drives local charge redistribution within the Ru-O framework. Consequently, at an optimal Zr content of ∼0.3, this modulation optimizes OER intermediate adsorption, stabilizes the oxygen framework, and suppresses RuO4-like species. The optimized Ru0.7Zr0.3O2 anode exhibits superior PEMWE performance, with cell voltages of 1.57 and 1.77 V at 1.0 and 3.0 A cm−2, and a specific energy consumption of 44.28 kWh kg−1 H2, surpassing the U.S. DOE 2026 target of 48 kWh kg−1 H2. Additionally, the catalyst demonstrates stable operation for over 200 h at 1.0 A cm−2. This work establishes lattice expansion induced charge redistribution as an effective strategy to simultaneously enhance the activity and durability of ruthenium oxide for PEMWE.

Sodium-ion batteries (SIBs) are emerging as promising alternatives to lithium-ion technology for energy storage, driven by the cost-effectiveness and sustainability of sodium resources. However, a persistent challenge lies in developing layered oxide cathode materials that simultaneously exhibit high energy density and robust moisture stability. In this work, we demonstrate an orbital-hybridization regulation strategy to concurrently address these limitations by reinforcing Na-O bonds. This regulation is effectively achieved through the incorporation of Ti, Sn, and Li metals (without single d electrons) into the transition metal (TM) slabs. This reduces the hybridization between TM 3d and O 2p orbitals, thereby restricting the gliding of the TMO2 slab and preventing spontaneous Na+ extraction from a model compound O3-Na0.85Ni0.40Mn0.60O2. Consequently, the phase evolution, previously observed as a complex sequence of O3 - O ' 3 -P3 - P ' 3 - P3 '- O3 '- O1, is simplified. Furthermore, the deleterious and spontaneous P-to-O phase transition, which typically occurs under deep desodiation conditions, is completely suppressed. As a result, the synthesized O3-Na0.85Ni0.40Mn0.35Ti0.2Sn0.03Li0.02O2 cathode exhibits superior electrochemical performance and significantly enhanced air stability. This research provides valuable insights into an effective orbital-hybridization regulation approach for developing high-energy and highly stable cathode materials suitable for advanced rechargeable batteries.

Graphitic carbon nitride (g-C3N4, CN) holds promise for photocatalytic hydrogen evolution, yet its performance is fundamentally hindered by inefficient directional transport of photoexcited charge carriers and intrinsically sluggish kinetics for the adsorption and reduction of protons (H*). Herein, we fabricated a ternary photocatalytic system by first constructing a 2D/2D Ti3C2/CN Schottky junction via facile ball-milling, followed by the decoration of Rh single atoms (SAs) onto its surface in the form of Rh-N4 and Rh-O3 moieties via photoreduction. Density functional theory calculations reveal that the Rh SAs both narrow the bandgap of CN and downshift the p-band centers of coordinated N and O atoms relative to the Fermi level, thereby optimizing hydrogen adsorption Gibbs free energy (Delta GH*), in which the Delta GH* of coordinated N and O atoms reaches a value of -0.46 and -0.04 eV, respectively. As evidenced by femtosecond transient absorption spectroscopy, photoexcited electrons in the RhSA-Ti3C2/CN composite undergo rapid interfacial transfer across the Ti3C2/CN Schottky junction within 33.5 ps, followed by ultrafast migration to the Rh sites in just 1.9 ps. Consequently, the optimal 0.25 wt% Rh3 wt% Ti3C2/CN photocatalyst achieves a hydrogen evolution rate of 1195.5 mu mol h- 1 g- 1 under visible light, surpassing pristine CN and the binary Ti3C2/CN junction by factors of 102 and 11, respectively. This work demonstrates that the integration of SAs with nanoscale heterojunctions not only enables ultrafast directional charge migration but also optimizes the adsorption energetics of key intermediates, thereby offering a generalizable design principle for high-performance CN-based photocatalysts and beyond.

The Fe(III)|Fe(IV) redox couple in iron-containing Na layered oxides enables high-capacity, cost-effective positive electrodes. However, although a high iron content (when the Fe concentration exceeds 33 at.% on transition metal layers) leads to rapid capacity decay during battery cycling, the underlying mechanism of this detrimental behaviour remains unclear. Here we report that the electrochemomechanical failure mechanism in Fe-rich Na layered oxides is related to the stability of the Fe octahedral coordination environment at the nanoscale. Fe-ion migration and dissolution govern the formation of intragranular microcracking in the positive electrode active material particles, accompanied by dislocations and an uneven distribution of mechanical stress. Driven by the non-uniform strain field, microcracks proliferate and planar gliding occurs, resulting in a stepped surface. By nanoscale doping with Al(III) (1 at.%), Y(III) (1 at.%) and Co(III) (3 at.%), we inhibit the Fe-ion migration and dissolution, thereby reducing cracks and planar gliding. Using the multi-element nanoscale-doped iron-rich sodium layered oxide at the positive electrode and a hard-carbon-based negative electrode, we assembled and tested 2.7-Ah Na-ion pouch cells showing an initial specific energy of 121 Wh kg-1 (based on the total mass of the cell) at 26 mA g-1, and a discharge capacity retention of 83.4% after 2,000 cycles at 130 mA g-1 at 25 °C.

High-density glass has emerged as a viable alternative for next-generation scintillation applications owing to its exceptional physical and chemical stability, in addition to its cost-effectiveness. A series of Ce3+-activated gadolinium gallium borosilicate (GGBSx) glass scintillators was synthesized via vacuum melt-quenching. With the Gd2O3 content increases, both the density (5.86 to 6.05 g/cm3) and molar volume (36.43 to 39.79 cm3/mol) exhibit a steady increase. The structural characteristics of the glass system were elucidated through extended X-ray absorption fine structure (EXAFS) analysis. GGBS1 glass exclusively includes Ce3+, which adopts a hexahedral [CeO6] configuration, whereas Gd exhibits both hexahedral and octahedral coordination configurations, characterized by a bond length of 2.35±0.1 Å and a σ2 of 0.0122±0.0015 Å2. In addition, as the Gd2O3 content grows, the shallow trap depth escalates from 0.804 to 0.858 eV, whereas the deep trap depth initially ascends from 0.948 to 1.434 eV before subsequently declining to 1.010 eV. The GGBS1 glass exhibits a high transmittance of around 80

Green hydrogen production driven by intermittent renewable energy poses significant challenges to alkaline hydrogen evolution reaction (HER) in achieving high-efficiency and durability. An all-in-one nanostructured electrochemical reactor (NER) was newly designed and synthesized for the HER electrode to tackle the challenges by enabling continuous electron transport and intensified gas-liquid transport in NER, thereby maximizing the interfacial charge-transfer reaction capability of the catalyst electrode under large and varying currents. This was realized by designing an all-in-one catalyst P-CoPt3/P-CoMoO4, featuring a self-supported structure, a heterostructure, and a super-hydrophilic nanoarray. This all-in-one catalyst functions as a built-in NER with finely-tailored critical interfaces. Self-supported structure and heterostructure form strong couplings at electron-conducting heterointerfaces, enabling continuous electron transport across these interfaces and thus in the NER. Super-hydrophilic nanoarray allows continuous gas-liquid transport at electrode/electrolyte interfaces, intensifying the gas-liquid transport process in the NER. Consequently, P-CoPt3/P-CoMoO4 displayed a >30-fold increase in mass activity for alkaline HER compared to the P-CoPt3 catalyst electrode. It exhibited an impressively low overpotential of 132 mV at 1 A cm-2. Stable operation for over 750 h at 100 and 500 mA cm-2 and notable durability under varying currents were also obtained. Overall water-splitting of P-CoPt3/P-CoMoO4 || RuO2 outperformed the commercial Pt/C || RuO2, especially at higher currents.

Precisely engineering the coordination shells of single‐atom catalysts (SACs) through defect control represents a powerful yet largely underexplored strategy to tailor their microenvironment and activity. Herein, Ru single atoms (SAs) and cadmium vacancies (V Cd ) are synergistically introduced into CdS nanoparticles coupled with Ti 3 C 2 T x MXene, forming Ru‐Cd 1‐x S/Ti 3 C 2 T x Schottky junctions with asymmetric Ru‒S 3 ‒V Cd motifs at both the surface and interface. Notably, the second‐shell V Cd cooperates with the Ru SAs to downshift the p‐band center ( ε p ) and optimize H 1s‐p antibonding orbital occupancy, enabling adjacent S sites to attain a near‐ideal hydrogen adsorption free energy (ΔG H* = −0.03 eV) and a ΔG 2H* value of 0.23 eV for the dihydrogen intermediate. Concurrently, V Cd ‐mediated Ru─O covalent bonds act as atomic bridges at the heterointerface, amplifying the built‐in electric field (BIEF) by 2.56 times and accelerating interfacial photoexcited charge transfer in 1.3 ps. With an ultralow Ru loading of 0.1 wt.%, the optimal Ru 0.1 ‐Cd 1‐x S/Ti 3 C 2 T x ‐1.5 wt.% composite achieves a photocatalytic H 2 evolution rate of 48.58 mmol g −1 h −1 , surpassing pristine CdS by a factor of 45.4, along with an apparent quantum efficiency (AQE) of 16.2% at 420 nm. This work establishes a new strategy for atomic‐level microenvironment engineering of SACs across both surfaces and heterointerfaces.

The critical progression of structural disorder, which governs the bulk glass-forming ability (GFA), can be elucidated as an ergodicity-breaking process. Understanding the atomic characteristics involved is imperative for establishing advanced glass design principles. However, conventional glasses present significant challenges due to their inherently complex and ambiguous disorder motifs, such as intricate and random atomic clusters or ring distributions. In this work, we synthesize a family of zero-dimensional hybrid metal halides with tunable short- to medium-range structural arrangements to form glasses with diverse GFAs. Through altering molecular shape and surface electrostatic potential of organic cations, their rotational order is able to be broken in a controlled manner. This leads to distinct phase space partitions of molecular movements, allowing for tunable GFAs. Our findings provide a fundamental design approach for synthesizing property-oriented glasses by controlling molecular rotational order, which can be applicable to a wide range of molecular glasses and amorphous solids. Revealing the structural features governing ergodicity breaking is critical to understanding glass formation. Here, the authors synthesise a family of hybrid metal halide glasses, and show that the molecular shape and polarity determine rotational disorder, enabling diverse glass-forming abilities.

ABSTRACT Paired electrolysis is being actively developed for co‐producing valuable chemicals by leveraging electron transfer at bipolar electrodes. In electrochemical CO 2 reduction to formate, if the reaction is coupled with oxygen evolution reaction, formate experiences severe crossover and oxidation to CO 2 over anode in membrane electrode assembly (MEA) electrolyzer. We reported a convergent electrolysis that produces formate at bipolar electrodes by coupling CO 2 reduction with biomass‐derived carbohydrate (for example, glucose) oxidation, maximizing the electron efficiency toward formate (0.88 formate per e − ) and suppressing oxidation of crossed formate at anode. This convergent electrolysis shows low electricity consumption for formate production (76.5 Wh mol −1 at 100 mA cm −2 ), lower than that of conventional CO 2 reduction (180−350 Wh mol −1 ). Furthermore, we extended the convergent electrolysis to acetate production by coupling electrochemical CO reduction with waste polylactic acid plastic oxidation. This work offers a framework for the rational design of paired electrolysis for low electricity consumption of chemical production.

The potential use of ammonia (NH3 ) as a hydrogen energy carrier has generated significant interest in developing efficient catalysts for producing NH3 under mild conditions. The main obstacles for NH3 synthesis are the activation of the N equivalent to N bond and the desorption of NH3 from the catalyst surface. Here, we report the use of C60 to overcome these challenges. Through electron transfer, migration, and feedback between C60 and Ru, there is a balance of electronic density at the Ru active sites and a shift in the d -band center. This simultaneously satisfies the electronic requirements for enhancing N2 activation while weakening NH3 adsorption, thereby circumventing the bottlenecks in NH3 synthesis under mild conditions. Meanwhile, anchoring of C60 accelerates hydrogen spillover and enhances the exchangeability of hydrogen species in the ZrH2 support, as well as expose a greater number of B5 sites of Ru entities, resulting in the co-optimization of hydrogen migration and nitrogen activation. As a consequence, the NH3 synthesis rate of the C60 -Ru/ZrH2 catalyst is approximately twice that of the Ru/ZrH2 catalyst at 400 degrees C and 1 MPa. This study shows that doping C60 represents a fundamentally different approach compared to traditional promoters for catalytic NH3 synthesis. We anticipate that this strategy may be generalized to generate widespread interest in the catalysis of NH3 synthesis. (c) 2026 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

The bonding strategy cannot effectively address the inherent limitations of layered nanozymes, resulting in their failure to maintain stability within the tumor microenvironment (TME). Herein, ammonium (NH4+)-intercalated δ-MnO2 nanozymes (N-MnO2) were constructed through the acid-base neutralization strategy. Due to interlayer van der Waals interactions, the NH4+ is stabilized in a nonbonded configuration. Significantly, nonbonding NH4+ exhibits unique electron-manipulating capabilities, enabling precise regulation of Mn 3d spin electrons from a high-spin state (t2g3eg1) to low-spin (t2g4eg0) configurations. The controlled spin-state redistribution prevents electron occupation in the eg antibonding orbitals (σ*), thereby significantly enhancing the stability of the Mn-O σ-bond and suppressing Jahn-Teller (J-T) distortions in the [MnO6] octahedra of layered MnO2. This dual nonbonding stabilization mechanism effectively resists structural disruption by endogenous glutathione (GSH, a scavenger of superoxide radicals), which can enhance the enzyme-mimetic activity. Furthermore, the nonbonding NH4+ in N-MnO2 maintains a dynamic Mn3+/Mn4+ equilibrium, endowing the nanozyme with dual catalase-like and oxidase-like activities. This can catalyze cascade enzymatic reactions (H2O2 → O2 → O2•-) to sufficiently enrich O2•-. Consequently, it is demonstrated that N-MnO2 possesses enhanced cascade catalytic performance within the complex TME for tumor-specific therapy.

Coal gasification fine slag (CGFS) is a solid waste with over 60% inorganics (SiO₂, Al₂O₃, Fe₂O₃). Current disposal by landfilling and stockpiling wastes resources and pollutes the environment, so resource utilization is economically and environmentally beneficial, especially as silicon-based materials show promise but face high production costs. In this work, mechanical activation and chemical modification are employed to convert the silicon fraction of CGFS into high-value lithium-ion silicon-carbon anode materials, enabling both efficient solid-waste utilization and significant cost savings in battery production. Spherical SiO₂ is first extracted from the inorganic components of CGFS via an ash-removal process; however, its poor conductivity and low initial coulombic efficiency limit practical application. To overcome these issues, pure silicon is synthesized through magnesiothermic reduction. Given that the volumetric expansion of pure silicon during charge-discharge cycling often leads to structural degradation and electrode failure, compromising cycle stability and safety, a carbon-coating strategy is adopted. Specifically, sucrose-a hydroxyl-rich carbon source capable of forming hydrogen bonds with the silicon surface-is used to construct silicon-carbon composites via in situ liquid-phase coating. This coating mitigates the expansion stress of silicon particles while enhancing overall conductivity. The resulting silicon-carbon anodes exhibit high specific capacity and excellent long-term cycling performance, offering a viable technical pathway for the sustainable valorization of CGFS.

Ru-based catalysts have attracted increasing interest due to their high efficiency in NH3 synthesis, yet their performance is limited by the inability of single site to simultaneously activate both N2 and H2 molecules. To overcome this challenge, introducing different functional sites (e.g., C60 as an adsorption/activation site for H2) is vital to achieving highly efficient NH3 synthesis under mild conditions. However, how the relative positioning of the second functional site to the Ru site influences the local environment and subsequent catalytic performance is still elusive. Herein, we present a site-selective strategy for anchoring C60 at distinct locations on a single-site Ru catalyst. Compared to surface-anchored C60, embedded C60 substantially modifies the electronic structure of the Ru single-atom site and decreases the work function. By virtue of cascading different functional sites, embedded C60 facilitates hydrogen spillover to nitrogen species activated on Ru to form NH3. In contrast, despite the high capacity for H2 adsorption, surface-anchored C60 exhibits sluggish hydrogen spillover, which results in its inefficient catalytic performance. Therefore, the optimal single-site Ru catalyst with embedded C60 achieves a 1.4-fold increase in the NH3 synthesis rate compared to its counterpart with surface-anchored C60 at 400 degrees C and 1 MPa. This study sheds light on optimizing the positioning of second functional site in the design of highperformance NH3 synthesis catalysts.