NH4V4O10 (NVO) is a promising cathode for aqueous zinc-ion batteries (AZIBs) owing to its large interlayer spacing and multielectron redox chemistry, but its practical use is hindered by unstable oxygen vacancies, vanadium dissolution, and sluggish kinetics. Here, we propose a thermodynamically favorable fluorine (F)-refilling strategy to regulate the defect chemistry of NVO and obtain an F-modified cathode (denoted NVOF). Instead of simply creating vacancies, the introduced F atoms preferentially occupy oxygen-deficient sites and form stable VF bonds, thereby reconstructing the local coordination environment and stabilizing the defect structure during cycling. Combined experiments and theoretical calculations demonstrate that F refilling stabilizes oxygen-vacancy structures, reduces interlayer interactions, lowers Zn2+/H+ migration barriers, and enhances structural stability by suppressing irreversible deammoniation and vanadium dissolution. These effects collectively accelerate Zn2+ storage kinetics and improve structural durability. As a result, the optimized NVOF-3 cathode delivers a high reversible capacity of 503.4 mAh g−1 at 0.5 A g−1, retains 243.2 mAh g−1 at 20 A g−1, and shows stable cycling over 10,000 cycles. The assembled quasi-solid-state zinc-ion batteries also exhibit remarkable electrochemical performance over a wide temperature range from −30 to 60 °C and demonstrate strong potential for wearable electronics. This work offers an effective non-metal refilling strategy for stabilizing defect chemistry and designing durable, high-rate AZIBs cathodes.

Single-walled carbon nanotubes (SWCNT) possess outstanding electrical and mechanical properties, endowing them highly promising for thermoelectric (TE) energy conversion. However, their poor dispersibility and suboptimal doping state often disrupt the continuity of conductive networks and hinder the synergistic enhancement of electrical conductivity (σ) and Seebeck coefficient (S). Currently, green and eco-friendly dispersants have attracted increasing attention owing to their low cost, environmental compatibility, and biodegradability. Herein, we develop a facile strategy that utilizes biomass chitosan (Chs) as a dispersant followed by a post-treatment with sodium borohydride (NaBH4) to simultaneously optimize the dispersibility and doping state of the Chs/SWCNT composite. The interconnected conductive network with uniformly dispersed SWCNT is constructed through interfacial interactions between Chs and SWCNT, enabling efficient carrier transport and high σ. Subsequent NaBH4 treatment induces a dedoping effect, giving rise to enhanced S. Consequently, a maximum power factor of 291.5 ± 14.1 μW m−1 K−2 is achieved at a Chs loading of 20 wt% and a NaBH4 treatment of 1 mg mL−1 for 30 s, surpassing most of the previously reported CNT based composites. Furthermore, a thermoelectric generator assembled from the optimized Chs/SWCNT composite film demonstrates outstanding output power, excellent temperature responsiveness, and reliable signal encoding functionality. This work provides new insights into the development of high-performance and sustainable TE materials suited for multifunctional applications in next-generation smart electronics.

Early-age cracking of ultra-high-performance concrete (UHPC) arises from stage-wise volumetric deformation (plastic, autogenous and drying shrinkage). Here we develop a stage-matched control strategy using a plastic expansion agent (PEA), a superabsorbent polymer (SAP) for internal curing, and a CaO–CSA expansive agent (CEA). Each single admixture effectively suppressed shrinkage in its corresponding stage, but caused strength loss to different extents. After optimization, a ternary system (0.04% PEA, 0.05% SAP and 10% CEA, by binder mass) delivered synergistic multi-stage control: 1 d plastic, 7 d autogenous and 28 d drying shrinkage decreased to 4, 103 and 140 µε, giving 161 µε total shrinkage at 28 d. XRD, MIP and SEM show slightly increased porosity yet stabilized long-term deformation, while maintaining 130.8 MPa compressive strength at 28 d. This time-domain compensation offers a practical balance between volumetric stability and mechanical performance for crack-sensitive UHPC elements.

ABSTRACT Single‐atom alloy (SAA) catalysis research often reports that a SAA catalyst, in the general formulation of a single‐atom metal M1 alloyed on the surface of the host metal M2, facilitates a probe reaction. However, for catalytic reactions that present decoupled rate‐ and selectivity‐limiting steps, the alloying site density may significantly manipulate these independent steps, but it has rarely been explicitly examined for any SAA systems. Herein, using the electrocatalytic CO reduction as a probe reaction, we report that the nominal Pd 1 Cu cube SAA catalysts exhibit distinctive high reactivity toward ethylene or ethanol, respectively, depending on whether the Pd atoms are in dilute or crowded forms. Although the presence of single‐atom Pd embedded on Cu uniformly promotes CHO* formation and C─C coupling, the dilute‐Pd 1 Cu favors ethylene formation by enabling low‐barrier C─O cleavage from a flat CH 2 CH 2 OH* intermediate, whereas the crowded‐Pd 1 Cu promotes ethanol formation by stabilizing an upright hydrogenation transition state of the same intermediate. Furthermore, we present evidence that the catalytic chemistry of crowded Pd 1 species differs from that of the Pd 2 ‐dimer; the latter, albeit unstable, steers reaction selectivity to acetate instead. These results uncovered the underappreciated importance of controlling SAA catalytic chemistry from the perspective of single‐atom site densities.

Ammonia decomposition is an attractive route for on-demand hydrogen production from carbon-free chemicals. However, the rational design of efficient catalysts remains challenging due to intrinsic trade-offs in surface reactivity: catalysts that effectively activate N-H bonds often bind reaction intermediates too strongly, leading to surface poisoning and sluggish product desorption. Ruthenium (Ru) is among the most active metals for this reaction, yet its strong nitrogen adsorption and scarcity limit its practical utilization. Here, we employed first-principles calculations to design single-atom alloys (SAAs), in which isolated Ru atoms are dispersed within 3d-5d transition-metal hosts to maximize the atom efficiency of Ru while potentially improving catalytic reactivity. We first evaluated the thermodynamic stability of various Ru-doped SAAs against dopant aggregation and subsurface segregation. We then systematically investigated the reaction energetics of ammonia decomposition, focusing on the trade-off between ammonia dehydrogenation and the associative desorption of N2 and H2. Thermodynamic screening identified Ru/Fe, Ru/Co, and Ru/Ni SAAs as promising candidates with favorable energetics for associative desorption. Notably, further kinetic analysis revealed that Ru/Fe SAA is highly active for ammonia decomposition, exhibiting reduced barriers for both dehydrogenation and associative desorption compared with pure Ru. In addition, we identified the adsorption energy of atomic nitrogen as an effective thermodynamic descriptor correlating well with catalytic reactivity across the SAAs. This work provides fundamental insights into overcoming catalytic limitations through atomic doping strategies, while demonstrating how SAAs maximize the atomic efficiency of scarce noble metals and guiding the design of more efficient catalysts for ammonia decomposition.

The in situ exsolution of nanoparticles (NPs) has brought new opportunities for the application of perovskite-based catalysts in solid oxide electrolyzers. However, the kinetic driving force controlling cation migration and subsequent metal nucleation is not yet fully understood. Here we identified surface electrostatic gradient as the decisive kinetic factor in governing metal exsolution by treating La0.3Ca0.6Ti0.9Mn0.05Ni0.05O3-δ (LCTMN) with NaBH4 of different concentrations. Multi-scale characterizations revealed that different spatial distribution of surface oxygen vacancy induced positive surface potential shift and established electrostatic gradients that attracted Ni2+ cations toward LCTMN surface, thereby driving Ni2+ migration and reduction. Moreover, theoretical calculations demonstrated that surface oxygen vacancies reduced Ni segregation energy and work function of LCTMN, elucidating the critical role of electronic redistribution in accelerating in situ exsolution. Consequently, treatment of LCTMN with 3.0 M NaBH4 yielded a high-density dispersion of uniform Ni NPs with abundant strongly anchored interfacial sites for CO2 adsorption and activation. Notably, it delivered maximal current density of 1.25 A cm-2 and CO Faraday efficiency of 94.23%, coupled with a superior 100-hour stability, surpassing all counterparts. This study establishes a direct link between surface potential and exsolution kinetics, providing a universal paradigm for designing high-performance perovskites with desirable reactivity.

When catalyzing a reaction comprising elementary reaction steps that demand both strong and weak adsorption of sequential intermediates to complete a full cycle, catalytic metals often exhibit reactivity compromises, known as Sabatier constraints. Herein, computational and experimental findings suggest that dynamic modulation of the catalyst spin state can provide a new handle to overcome such limitations via low- and high-spin catalysis for ammonia decomposition, which is a reaction that exemplifies Sabatier constraints due to the difficulty in achieving strong NH3 binding as well as weak *H and *N binding for efficient H2 and N2 formations, respectively. We demonstrate that the self-heating ferrimagnetic Ru/Fe3O4 catalyst operating under an alternating magnetic field (AMF) exhibits at least a 5-fold enhancement in activity relative to standard thermal operation below 400 °C. The key benefit comes from the time-varying magnetic flux within the catalyst under AMF, enabling rapid electronic responses at the Ru sites that mitigate Ru nitridation by transiently inducing a high-spin configuration of the metal. These findings highlight AMF-driven catalysis as a general reaction strategy for dynamically regulating catalyst electronic states and, in turn, surface intermediates, thereby overcoming the often-encountered Sabatier constraints in various catalytic reactions.

Catalytic conversion of one-carbon (C1) molecules, such as CH4, CO2, and CO, into fuels and value-added chemicals is a vitally important process in the chemical industry. The C1 catalytic reactions, including methane steam reforming and CO/CO2 hydrogenation for methanol synthesis or liquid fuel/chemicals production based on the Fischer-Tropsch technology, are foundational to the conventional chemical/energy industry. Additionally, these C1-related catalytic reactions have also been identified as important platforms for the power-to-X (PtX) processes. By utilizing CO2, biogas, or waste CH4 as the carbon sources, C1 catalytic reactions facilitate the creation of synthetic fuels and valuable chemicals, effectively recycling carbon and reducing reliance on fossil resources. However, conventional C1 catalytic reactions are typically operated at a very large scale and under a steady state for centralized production. For the PtX application, electrified and/or dynamically operated C1 catalytic processes for distributed synthesis must be developed in order to use intermittent renewable electricity to drive the reactions. This perspective summarizes recent advances and discusses the opportunities and challenges of the conversion of C1 molecules through electrified and dynamically operated catalysis.

Single-atom catalysts and related materials offer great potential for selective, sustainable catalysis, but developing stable and uniform catalysts suitable for large-scale application remains challenging. This Voices article shares perspectives from six researchers on opportunities in the field to bridge fundamental studies and industrial application, in order to unlock the potential of these fascinating catalysts.

The scarcity of cost-effective and durable iridium-free anode electrocatalysts for the oxygen evolution reaction (OER) poses a significant challenge to the widespread application of the proton exchange membrane water electrolyzer (PEMWE). To address the electrochemical oxidation and dissolution issues of Ru-based electrocatalysts, an electron-donating modification strategy is developed to stabilize WRuOx under harsh oxidative conditions. The optimized catalyst with a low Zirconium doping (Zr, 1 wt.%) enhances durability noticeably, with a 77% reduction in degradation rate in the durability test of 10 mA cm-2 in 0.5 m H2SO4. When integrated into a homemade PEMWE device, the Zr-doped catalyst achieves excellent long-term stability, lasting up to 650 h at 100 mA cm⁻2. Additionally, the electronic modulation from the Zr modification leads to superior activity with a low overpotential of 208 mV at 10 mA cm-2. Theoretical calculation results further reveal that electron-donating Zr modification effectively suppresses Ru overoxidation and lattice oxygen participation, maintaining a robust structure during acidic OER. This modification also promotes deprotonation through stronger Brønsted acid sites, significantly improving both long-term stability and activity.

To solve the stability of Pt nanoparticles in Pt-based electrocatalysts, herein we demonstrate an electrocatalyst (Pt/FeSA-NC) featuring with Pt nanoparticles deposited on Fe single-atom nitrogen-doped carbon, which was realized by the pyrolysis and subsequent wet chemical reduction approach. The as resultant Fe single-atom nitrogen-doped carbon exhibits delicate dodecahedral structure with uniformly distribution of Pt nanoparticles which provide suitable surrounding environment for Pt nanoparticles and enable the intense interaction between atomic Fe and Pt. Electrochemical results shows a superior activity with overpotentials reaching up to 19 mV and 189 mV, respectively at current densities of 10 and 100 mA cm-2, outperforming commercial Pt/C (27 mV and 229 mV) in alkaline conditions. DFT calculations revealed a nearly thermal neutral Delta GH* value of-0.360 eV of Pt/FeSA-NC, therefore, reducing the energy barrier and ensuring an accelerated reaction thermodynamics. This research offers a new approach to resolve the stability challenges of Pt-based electrocatalysts and advances the advancement of highly efficient electrocatalysts.

Perovskite cathodes for CO2 electrolysis offer excellent redox stability but suffer from limited activity. Although in situ exsolution of B-site cations is a powerful strategy to alleviate this issue, this process often triggers co-segregation of insulating AOx phases, which diminishes active site exposure and ionic-electronic conductivity. Here we addressed the critical issue of insulating phase segregation in conventional exsolved perovskite by developing a Ce-doping strategy in Sr1.95Ce0.05Fe1.3Ni0.2Mo0.5O6-delta (SCeFNM). This material, upon annealing in a reducing atmosphere, allowed in situ construction of nanoscale CeO2-NiFe/oxide heterostructures (CeO2-NiFe@SCeFNM) by co-exsolving oxygen-deficient CeO2 phase and NiFe alloy nanoparticles (NPs) on the surface. The unique architecture achieved a high current density of 1.57 A cm-2 at 1.5 V and 850 degrees C with a CO faradaic efficiency of over 96%, outperforming NiFe@SFNM and their counterparts. Combined results demonstrated that the superior activity mainly came from the synergy within the "three-in-one" heterostructure, where NiFe alloy NPs increased the electronic conductivity, and CeO2 phase extended the O2- migration channels capable of enhancing CO2 adsorption and activation, while the perovskite backbone ensured structural integrity. This study establishes a universal paradigm for constructing advanced catalysts for diverse applications via co-exsolution of metal NPs and defective oxide phases from appropriately A-site-doped perovskites.

The development of substrates capable of anchoring single-atom catalysts (SACs) while enabling their dynamic reconfiguration into heteronuclear dual-atom catalysts (DACs) holds considerable promise for electrochemical synthesis, yet remains underexplored. Here we show that electrochemical desulfurization of MoS2 generates vacancy-rich 1T' domains, which support high loadings of Cu (7.9 wt%) and Pt (6.7 wt%) SACs that are well-positioned for dynamic sintering to form DACs. Operando X-ray absorption spectroscopy and density functional theory calculations reveal a voltage-driven, reversible transformation between individual Pt/Cu SACs and Cu-Pt DAC configurations during hydrogen evolution reaction potentials. The electric-field-induced Cu-Pt DACs exhibit superior performance in the selective hydrogenation of alkynes compared with their monometallic SAC counterparts. This work underscores vacancy-enriched 1T'-MoS2 as a versatile platform for high-density SAC deposition, enabling on-demand structural reconfiguration and paving the way for tailored catalyst design in electrosynthesis.

The rising level of CO2 concentration in the atmosphere poses major threats to the global climate and environment. Various technologies have been developed to mitigate its negative effects through non-conversion and conversion routes. Particularly, solid oxide electrolysis cells (SOECs), as a promising technology with the highest energy efficiency, have garnered considerable attention for their effectiveness to electrochemically convert CO2 into high-value fuels. However, the insufficient catalytic activity, poor long-term stability, and high costs have significantly hindered the industrial-scale application of SOECs. To this end, substantial efforts, with an emphasis on the smart design of targeting electrode materials for specific applications have been devoted to advancing the electrosynthesis of high-value fuels from CO2 in various SOECs, but there still lacks a critical and comprehensive review in-depth discussing the fundamentals, and summarizing the latest advances in various applications and electrode materials for electrochemically converting CO2 to high-value fuels in SOECs. This review thus aims to fill this gap by focusing on the fundamentals (i.e., SOEC working principles, thermodynamics, kinetics and representative evaluation parameters), specific applications (i.e., pure CO2 electrolysis, CO2-H2O co-electrolysis, fuel-assisted CO2 conversion), and material selection criteria (i.e., cathodic materials for CO2 conversion, and anodic materials for fuel-assisted CO2 conversion). In addition, the challenges that this technology is currently facing, and our perspectives on electrochemical CO2 conversion in SOECs are proposed to guide the smart design of high-performance electrocatalysts and future industrial-scale application of SOECs for electrosynthesizing high-value fuels from CO2.

The accumulation of inactive by‐products caused by the parasitic side reaction on cathode side is an overlooked question leading to performance degradation of zinc‐ion batteries. In this research, taking the MnV 2 O 4 as a model, an amorphous carbon interphase is proposed as a pre‐implanted cathode‐electrolyte interphase (CEI) to design ultrafast‐kinetics MnV 2 O 4 @C cathode. It is noted that such CEI integrates hydrophobic and conductive characteristics, contributing to dissolution shielding, continuous interfacial conductive channel, and thus preventing inactive by‐product accumulation on the cathode interface. Unexpectedly, such electrode shows superior storage performance at a wide temperature range of −20–55 °C. It can deliver a specific capacity of 253.3 mAh g −1 at the high current density of 10 A g −1 even after 8000 cycles. Moreover, a high specific capacity of 393.8 mAh g −1 (0.1 A g −1 ) can be retained after 300 cycles at 55 °C, as well as 205.1 mAh g −1 at the condition of −20 °C and 5 A g −1 . Beyond that, flexible solid‐state zinc‐ion batteries based on MnV 2 O 4 @C cathode with excellent wide temperature performance are demonstrated. This work highlights the importance of eliminating the dead by‐product effect to design advanced cathode materials for zinc‐ion batteries.

AbstractProton exchange membrane water electrolyzer (PEMWE) is of great importance for the production of green hydrogen. The large‐scale implementation of PEMWE, however, is seriously impeded by the sluggish oxygen evolution reaction (OER) at the anode, which results in considerable overpotential and thus the decreased energy conversion efficiency. To overcome this problem, researchers have extensively explored efficient anode catalysts that possess high activity and prolonged stability. Up to now, Ir‐based and Ru‐based catalysts are considered to be the most efficient candidates. Especially perovskite‐based catalysts have received intensive attention due to their distinctive structures and exceptional OER catalytic performance. To further promote their practical application, considerable research efforts are devoted to structural engineering toward enhanced activity and stability. In this paper, a review of the research progress on the advanced design of Ir‐ and Ru‐based perovskite catalysts is presented, with a focus on phase engineering, doping/substitution, morphology control, and compositing with other materials for perovskite catalysts as well as some preparation methods commonly used. It also summarizes the challenges and opportunities concerning perovskite‐based catalysts in current research, yielding further comprehension of the pertinent preparation and scrutiny of perovskite catalysts in the future.

Atomically dispersed metals on oxide supports with different distribution positions or coordination environments can dictate the reactivity; they have therefore attracted tremendous attention recently. Nonetheless, the acknowledging and understanding of different single atoms remain challenging due to the reactivity controversy of the supported single atoms and clusters or nanoparticles, particularly on the widely used ceria supports. Herein, by modulating the loading amount of Pt single atoms carefully with strong electrostatic adsorption on conventionally synthesized ceria supports, we obtained two different atomically dispersed Pt atoms with similar Pt-O coordination environments and CO adsorption characteristics. One is anchored on the surface of ceria, and it can migrate and aggregate once activated with reduction-reoxidation treatments. The other may be trapped by the surface defects or vacancies in ceria and would be fixed on the ceria support firmly in isolated states during activation. Despite the similar CO adsorption during the reaction, the former can catalyze CO oxidation in both the status of single atoms and aggregated PtOx clusters. However, the latter is inactive for the reaction and would not be affected by the activation treatment. It cannot involve the CO oxidation, resulting in the waste of supported Pt atoms.

The electrocatalytic reduction of CO2 to CO is slowed by the energy cost of the hydrogenation step that yields adsorbed *COOH intermediate. Here, we report a hydrogen radical (H center dot)-transfer mechanism that aids this hydrogenation step, enabled by constructing Ni-partnered hetero-diatomic pairs, and thereby greatly enhancing CO2-to-CO conversion kinetics. The partner metal to the Ni (denoted as M) catalyzes the Volmer step of the water/proton reduction to generate adsorbed *H, turning to H center dot, which reduces CO2 to carboxyl radicals (center dot COOH). The Ni partner then subsequently adsorbs the center dot COOH in an exothermic reaction, negating the usual high energy-penalty for the electrochemical hydrogenation of CO2. Tuning the H adsorption strength of the M site (with Cd, Pt, or Pd) allows for the optimization of H center dot formation, culminating in a markedly improved CO2 reduction rate toward CO production, offering 97.1% faradaic efficiency (FE) in aqueous electrolyte and up to 100.0% FE in an ionic liquid solution. Commercially viable catalytic CO2 electroreduction to CO would enable many green technologies, yet it is impeded by the initial hydrogenation step of CO2. Here, the authors report Ni-Cd dual atom catalysts with complementary properties of favorable adsorption of CO2 and H to overcome this barrier.