Ceramic cells promise ideal energy conversion and storage devices, making the development of efficient and robust air electrodes crucial for their application. In this study, a Ba0.4Sr0.5Cs0.1Co0.7Fe0.2Nb0.1O3-d (BSCCFN) air electrode, based on Ba0.5Sr0.5Co0.8Fe0.2O3-d (BSCF), is designed using a perovskite A-B-site ionic Lewis acid strength (ISA) polarization distribution strategy and is successfully applied in both oxygen-ion conducting solid oxide fuel cells (O-SOFCs) and proton-conducting reversible protonic ceramic cells (R-PCCs). When BSCCFN is used as the air electrode in O-SOFCs, a peak power density (PPD) of 1.45 W cm-2 is achieved at 650 degrees C, whereas in R-PCCs, a PPD of 1.13 W cm-2 and a current density of -1.8 A cm-2 at 1.3 V are achieved at the same temperature and show stable reversibility over 100 h. Experimental measurements and theoretical calculations demonstrate that low-ISA Cs* doping accelerates the reaction kinetics of both oxygen ions and protons, while high-ISA Nb5* doping enhances electrode stability. The synergistic effect of Cs* and Nb5* co-doping in the BSCCFN electrode lies in the ISA polarization distribution, which weakens the Co/Fe-O bond covalency, thereby promoting oxygen vacancy formation and facilitating the conduction of oxygen ions and protons. (c) 2025 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

Real exhaust streams rarely contain a single pollutant: NOx coexists with volatile organic compounds (VOCs) in flue gas from petrochemical production, chemical manufacturing, and waste incineration, yet catalysts that couple NH3-SCR with VOC oxidation typically suffer competitive adsorption, sulfur poisoning, and HCN byproduct formation. Here we engineer an epitaxially stabilized CuO overlayer on Ti1-xInxO2 that breaks the activity-selectivity-stability constraint by creating electron-poor, high-symmetry Cu-O sites and activating lattice-oxygen redox at the oxide-oxide interface. Interfacial strain and charge transfer increase Cu-O covalency and Lewis acidity, accelerating NOx reduction via an Eley-Rideal pathway while diverting sulfate deposition away from Cu. Concurrently, interface-activated lattice oxygen sustains deep oxidation of CH3SH (a representative S-VOC) through a Mars-van Krevelen cycle, suppressing HCN. Epitaxial interfaces thus offer a general route to poison-resistant multipollutant catalysis.

Amorphous iridium oxide (IrOx) is among the most active Ir-based catalysts for the acidic oxygen evolution reaction (OER), yet its stability is severely limited because lattice-oxygen participation often triggers irreversible oxygen loss that leads to iridium dissolution and structural degradation. Here, we present a surfactant-directed synthesis of mesoporous IrOx electrocatalysts featuring a hollandite-type local structure. This unique structure creates an atomic-mesoscale synergy that enhances OER activity without sacrificing stability and improves high-current-density performance. At the atomic level, the hollandite-type local structure promotes high OER activity and corrosion resistance. In situ spectroscopic and isotopic labeling experiments reveal a reversible cycle of lattice oxygen loss and reformation during OER. This process enables the flexible iridium local structure to transition between an initial six-coordinate state and a low-coordinated active state. At the mesoscale, an interconnected porous network ensures efficient mass transport and maximizes active-site accessibility. As a result, this mesoporous electrocatalyst achieves a low cell voltage (1.75 V @ 2 A cm-2) and excellent stability for more than 2000 h (@ 2 A cm-2) in proton exchange membrane water electrolysis (PEMWE).

Both heterojunction and core-shell photocatalysts have demonstrated promising performance in photocatalytic CO2 conversions to fuels. However, fundamental knowledge of heterojunctions in core-shell structures is highly desired to facilitate the design of future photocatalysts. By combining advanced experimental characterizations and density functional theory (DFT) calculations, the role of the Cu2O@MoS2 heterojunction in photocatalytic CO2 conversions to fuels was investigated. We discovered that the charge dynamics and electron transfer properties of Cu2O@MoS2 photocatalysts are altered by the heterojunction and Cu2O underlayer due to the electron transfer from Cu2O to MoS2 and the change in CO2 adsorption strength on the hybrid catalyst surface. Consequently, more electrons can travel to the surrounding liquid environment to be consumed by CO2 reduction. This study provides experimental and theoretical investigations of the fundamental mechanisms of heterojunction core-shell photocatalysts.

The operational instability of IrRu-based anodes, particularly under the dynamic regimes inherent to renewable energy, remains a critical barrier to cost-effective proton exchange membrane water electrolysis. Here, we address this challenge by designing hollandite-structured IrRuOx nanocrystals (H-IrRuOx) via a low-temperature phase-transition synthesis. Distinct from the conventional rutile structure, the open hollandite framework stabilizes sub-4-valent metal sites within a unique coordination environment, which simultaneously enhances the oxygen evolution reaction activity and suppresses metal dissolution by mitigating overoxidation. When integrated into membrane electrode assemblies, the H-IrRuOx catalyst layer demonstrates exceptional durability, operating stably at industrial current densities (1-2 A cm-2) with a minimal voltage decay rate of <4 µV h-1 over 3700 h. Crucially, under harsh dynamic cycling, it retains 96% of its initial activity after 36 000 cycles, outperforming conventional benchmarks. This structural engineering strategy provides a viable path to durable, cost-effective hydrogen production under realistic conditions.

IrO2 is a commonly employed anode catalyst for CO2 electrolysis in membrane electrode assembly (MEA) systems. However, under high current densities, its structural reconstruction leads to activity loss and stability degradation, limiting the industrial viability of CO2 electrolysis. Herein, we demonstrated a confinement reconstruction strategy to precisely regulate the structural evolution during electrolysis. Ethylene glycol serves as a structural modulator, protecting the catalyst surface, suppressing soluble species formation, and promoting ordered structural evolution. Single-atom Ru acts as a stability enhancer, forming robust Ir-O-Ru bridging structures that facilitate an ordered transformation from a 4-fold [RuO4]/[IrO4] to a 6-fold symmetry [RuO6]/[IrO6] octahedral framework, thereby enhancing structural rigidity and long-term stability. As a result, in MEA-based CO2 electrolysis, the catalyst achieves a stable operation at 200 mA cm(-2) for 480 h, maintaining a CO selectivity above 80%. Theoretical calculations further elucidate that the enhanced stability originates from the suppression of oxygen vacancy formation, making the lattice-oxygen-mediated mechanism (LOM) potentially less favorable. This work provides insights into the structural evolution of the OER catalysts under high-current-density conditions, paving the way for large-scale CO2 electrolysis commercialization.

Interfacial compatibility across multiple material parts governs device stability in solid-state batteries, flexible electronics, and high-temperature fuel cells. For thermoelectric devices, researchers principally focused on chemical reactivity and mechanical properties of material components, whereas precise control of the coefficient of thermal expansion (CTE) remains elusive. Here, we propose an innovative strategy using negative-thermal-expansion (NTE) particles to regulate CTE and resolve interfacial incompatibility. Incorporating predesigned interface reaction-free NTE particles into Bi2Te3-based, Mg3Sb2-based, and PbTe-based materials effectively improves thermoelectric performance, alleviates thermal stress, and enhances interfacial stability across a broad temperature range (300 to 800 kelvin). Notably, the NTE-modified Mg3(Sb,Bi)2/Bi0.4Sb1.6Te3 two-pair module achieves a record-high conversion efficiency (η) of 8.4% at ΔT = 350 K with a 71% interfacial thermal stress reduction, maintaining a stable interface and unchanged η throughout 1000-hour (42 days) thermal cycling. Our strategy establishes a universal approach for improving interfacial compatibility in high-temperature functional modules including thermal-barrier coatings and solar thermophotovoltaic devices.

This study presents a phase-regulation strategy for enhancing the thermoelectric performance of BiSbSe3-based materials through the controlled formation of a semiconductor-semimetal heterostructure. By incorporating sulfur and aluminum dopants, a hexagonal phase is induced within an orthorhombic BiSbSe3 matrix, thereby establishing a bidirectionally adjustable phase composition through compositional regulation. The hexagonal phase exhibits semimetallic behavior, with a Fermi level positioned higher than that of the semiconductor matrix. This electronic structure difference is consistent with low-barrier interfacial charge transfer and a modulation-doping-like redistribution of electrons across the phase boundaries, contributing to enhanced carrier concentration without severely sacrificing carrier mobility. Moreover, the inherently low thermal conductivity of both phases, combined with enhanced phonon scattering at the interfaces and simultaneous control over grain refinement during phase regulation, effectively suppresses the lattice thermal conductivity. The resulting biphasic structure enables coupled regulation of electronic and thermal transport, synergistically improving thermoelectric performance, achieving a peak thermoelectric figure of merit (zT) of 1.50 at 773 K in Bi0.98Sb0.98Al0.04Se2.8S0.2 under the fixed 2 wt % CuI donor-additive condition. This improvement relative to BiSbSe3 materials demonstrates the effectiveness of phase engineering in decoupling electrical and thermal transport properties. These results highlight interface-engineered semiconductor-semimetal heterostructures as an effective design route for high-performance thermoelectric materials.

Regulating the activity and stability of high-entropy perovskite air electrodes is essential for their application in ceramic electrochemical cells, yet the underlying mechanisms remain unclear. In this work, a novel high-entropy perovskite, Gd0.2Pr0.2Ba0.2Sr0.2Ca0.2FeO3-δ (GPBSCF), is developed as a highly active and stable air electrode for both oxygen-ion conducting solid oxide fuel cells (O-SOFCs) and reversible protonic ceramic cells (R-PCCs). It is demonstrated that high-entropy doping increases Fe4+ content and structural symmetry, thereby elevating oxygen vacancy/hole concentration and enhancing catalytic activity. Concurrently, the induced lattice distortion improves structural stability and inhibits Ba/Sr surface segregation. Furthermore, the increased Fe4+ content, combined with the pinning effect induced by lattice distortion, synergistically reduces the thermal expansion coefficient. In O-SOFCs, a symmetric cell with GPBSCF exhibits a low polarization resistance of 0.08 Ω cm2 at 650°C and operates stably for 1000 h. In R-PCCs, a single cell demonstrates excellent durability over 680 h. This work provides fundamental insights into high-entropy optimization mechanisms, guiding the rational design of advanced Fe-based perovskite air electrodes for durable ceramic electrochemical cells.

The size-dependent electronic and phononic configurations of single atoms and nanoclusters enable tailored functionalities. Their synergistic effects also attract attention, yet precise control of anti-aggregation states during high-temperature operations poses formidable challenges in multiple fields such as fuel cells and thermoelectrics. Herein, we develop a solution-processed strategy to precisely incorporate Pt species as isolated atoms (Pt1) and sub-nanoclusters (Ptn, ∼1 nm) in Bi2S3. Notably, Ptn of 1 nm size exhibit significant advantages over larger-size counterparts in tuning electronic structure and optimizing charge transfer. Furthermore, Pt1 and Ptn scatter 1 Å- to 1 nm- wavelength phonon that is conventionally underexplored. The 1 nm Ptn exhibits distinct force constant as compared to 3 nm Ptn, leading to ultra-strong phonon Rayleigh scattering, which in turn significantly reduces thermal conductivity. The optimized Bi2S3-Pt1/Ptn composite achieves breakthrough thermoelectric performance, attaining a maximum zT of 1.02 at 773 K and single-leg conversion efficiency of 1.58%, both setting benchmarks for Bi2S3 systems. This strategy can also be extended to other thermoelectric material systems such as Bi0.4Sb1.6Te3, PbTe, or other fields including solid-state batteries and solar cells.

Optimization of the electronic structure of Ptδ+ 5d orbitals by using a well–defined coordination environment to increase the efficiency of alkaline H2O dissociation kinetics remains challenging. Herein, TiO2 quantum dots (QDs) were carefully introduced into a Pt/Co3O4 system to form Pt/QDs/Co3O4, which created a pool of high–density Pt clusters anchored on an emerging symbiotic oxide surface. The strong interaction between QDs and Co3O4 induced the redistribution of Pt 5d orbital electrons. Spectroscopic characterization and theoretical calculations revealed that the resulting dual–active centers (α–Pt–O–Co and β–Pt–O–Co) played a key role in balancing hydrogen adsorption and strengthening water dissociation. Therefore, the support effect of the symbiotic TiO2/Co3O4 oxides resulted in the Pt/QDs/Co3O4 catalyst having a mass activity 2.17 times higher than that of Pt/C at an overpotential of 200 mV. In addition, the Pt/QDs/Co3O4 required only 1.78 V to reach an industrial–level current density of 500 mA cm−2, and it achieved continuous robust operation for over 500 h in an anion exchange membrane water electrolyser. The results obtained after the extended synthesis of a Ru/QDs/Co3O4 catalyst confirm the universality of the proposed support. This work sheds light on the surface activity of metals through an investigation of a support–facilitated design for efficient catalysts.

Abstract As a pivotal industrial chemical, adipic acid (AA) is synthesizable through the electrocatalytic oxidation of cyclohexanol under ambient conditions, utilizing electrons as a clean oxidant. This approach circumvents the energy-intensive and environmentally detrimental nature of conventional petrochemical processes, thereby offering a sustainable alternative for AA production. However, existing electrocatalysts are often plagued by instability in alkaline media, and their structure-activity relationships remain poorly understood. Here, we report a novel [Ni36] nanocage-based metal-organic framework ([Ni9]-MOF) synthesized via a bottom-up strategy from discrete [Ni9]-clusters, exhibiting excellent stability in both strong alkaline (8 M NaOH) and acidic (1 M HCl) conditions. [Ni9]-MOF demonstrates superior AA production (0.1239 mmol h−1 cm−2 at 1.61 V), and maintains this high activity 25 cycles with negligible loss, surpassing all prior high-performance catalysts in durability. Mechanistic studies reveal a three-step oxidation pathway via cyclohexanone, 2-hydroxycyclohexanone, and 6-hydroxyadipic acid. DFT calculations indicate the MOF framework enhances the charge density at the active [Ni9] site, accelerating reaction kinetics. This work not only provides a rational design strategy for constructing highly stable MOFs, but also presents the first MOF-based electrocatalyst for AA synthesis, opening new avenues for sustainable chemical production under mild conditions.

Electrocatalytic nitrate reduction reaction (NO3RR) is an important route for achieving both sustainable ammonia synthesis and wastewater treatment. However, the weak electron correlation characteristics between the active sites in traditional catalysts leads to their limited dynamic adaptability, which highly restricts the construction of ammonia synthesis systems that simultaneously possess high selectivity, high yield rate, and high stability. Here, we synthesize a NiCoFeOOH multi-metallic catalyst with strong electron coupling characteristics by inducing the electron-spin-geometric structure transformation via an in situ reconstruction strategy. NiCoFeOOH sustains high Faradaic efficiencies (FEs, 95%-99%) across a broad potential range together with a remarkable yield rate of 52 mg h-1 cm-2. The catalyst remains stable for up to 324 h at the industrial current density of 1 A cm-2 (FEs ∼ 90%, a record-breaking yield rate of ∼72 mg h-1 cm-2) in a membrane electrode assembly electrolyzer (MEA), ranking it among the most efficient and stable electrocatalysts reported hitherto. Operando/in situ characterizations combined with theoretical calculations show that atomic resonance between triple octahedral structural unit and key intermediate highly mediates the hydrogenation pathway. Based on the quantum spin exchange interaction, the adaptive charge transport channel among multiple atoms accelerates the proton-coupled electron transfer kinetics and suppress atomic dissolution at ampere-level current densities.

Electrides, with their unique electron-rich architectures, hold transformative potential for catalysis but face critical challenges in electrochemical systems due to inherent instability and synthesis limitations. Here, we present a kinetically controlled gas-solid reaction to synthesize phase-pure Ti3O electride nanoparticles, which exhibit high electrical conductivity (617 S cm-1) and broad electrochemical stability window (-0.4 to 2.1 V vs RHE) in acidic media. When used as a support for iridium (Ir) nanocatalysts in the oxygen evolution reaction (OER), the Ti3O electride demonstrates strong metal-support interactions. These interactions suppress both amorphization and coalescence of the Ir nanoparticles during the OER. Furthermore, Ti3O promotes oxygen diffusion into the Ir lattice, leading to the formation of subsurface oxygen-confined Ir nanoparticles, a previously unobserved catalytic active phase. This unique configuration shifts the OER mechanism entirely to the adsorbate evolution mechanism (AEM), avoiding participation of the lattice oxygen mechanism (LOM). Consequently, the Ir/Ti3O catalyst exhibits superior activity and stability compared to pristine Ir nanoparticles or Ir nanoparticles supported on other nonelectride titanium oxides, across both three-electrode cells and proton exchange membrane water electrolyzers. This work establishes electrides as versatile mediators for electronic structure engineering in electrocatalysis, enabling the stabilization of catalytic phases unattainable with conventional supports.

The paired electrochemical refining process of glycerol electrooxidation reaction (GEOR) coupling with cathodic hydrogen evolution reaction (HER) in anion exchange membrane electrolyzer (AEME) has attained extensive attention, because it can realize the decentralized co-generation of value-added chemicals and hydrogen. However, the high bond energy of C(sp3)-H bonds in glycerol put a formidable challenge to realize the sufficient activation. This seriously hinders the enhancement of single product selectivity and hardly obtains high current density for the AEME. Herein, we design Ni3B metallene to drive glycerol-to-formic acid (FA) conversion for GEOR. Furthermore, Ni3B metallene as anodic GEOR catalyst and commercial Pt/C as cathodic HER catalyst in AEME exhibit high glycerol conversion (97.1 %), yield 96.5 g FA product, and obtain 81.7 L H2 for 75 h under 0.5 A/cm2. Theoretical calculation, in situ Raman, and X-ray absorption near-edge structure spectroscopy results demonstrate that the decreased d-p band center distance at Ni3B metallene-derived BOx-NiOOH active phase, obtained by surface reconstruction, unlocks the lattice oxygen, promoting the C-H bond activation of glycerol reactant/glyceraldehyde intermediate, reducing the energy barrier of rate-determining step (dehydrogenation of glyceraldehyde) for GEOR, and thus improving the overall catalytic performance of AEME.

Maximizing the average figure‐of‐merit ( ZT avg ) of thermoelectric (TE) materials is crucial for optimizing the module performance. Herein, this work enhances the ZT avg to 1.42 (298–673 K) in a n‐type Mg 3 (Sb, Bi) 2 ‐based material by a stepwise optimization strategy. Specifically, Cr injects electron into Mg 3 Sb 0.8 Bi 1.19 Te 0.01 , which synergistically boosts carrier concentration and forms an electron accumulation layer at the interface. Meanwhile, lattice softening and interfacial scattering suppress lattice thermal conductivity. A peak ZT of 1.72 at 673 K and ZT avg of 1.30 over 298–673 K are achieved for Mg 3 Sb 0.8 Bi 1.19 Te 0.01 –1.5 wt.% Cr. Then, through grain refinement and Se doping instead of Te, a delicate equipoise is reached between the power factor and the electronic thermal conductivity. Eventually, the Mg 3 Sb 0.8 Bi 1.19 Se 0.01 –1.5 wt.% Cr sample obtains an outstanding ZT of ≈1.9 at 573 K and ZT avg of 1.42 over 298–673 K. The integrated two‐pair full‐Zintl YbZn 2 Sb 2 /Mg 3 (Sb, Bi) 2 module achieves a high conversion efficiency of 10.5% and power density of 0.37 W cm −2 simultaneously under a temperature difference of 370 K. More importantly, this module exhibits excellent thermal stability during a 10‐day in situ test. This work provides new ideas for applications of full‐Zintl modules to the recovery of waste heat.

Zeolite-supported noble metal nanoparticle (NP) catalysts demonstrate distinctive properties in heterogeneous catalysis reactions. However, due to the limitations of conventional liquid-phase synthesis methods, understanding of the dynamic crystallization mechanism of zeolites on the microscopic scale is still limited. Importantly, it impedes the in-depth establishment of relationship between structure and reactivity. Herein, we successfully develop a unique solvent-free and organic template-free solid-phase synthesis strategy for preparing Pt/ZSM-5 encapsulated structures to investigate the time-resolved dynamic evolution of zeolite crystallization process. Using the time-resolved X-ray atom pair distribution function and the in-situ scanning electron microscopy technique, the "dissolution-recrystallization" transformation mechanism of structural evolution for zeolite is observed. This dynamic mechanism induces AlO 4 structural distortion in Pt/ZSM-5 encapsulated structure, triggering strong metal-support interaction. The enhancement of Br & oslash;nsted acid density and the cationic of Pt mediates the process of cracking of C-C bonds and hydrogenation of C=C bonds. Pt NPs confined in mesoporous pores of ZSM-5 improve the mass transfer efficiency of reaction intermediates. Therefore, Pt/ZSM-5 exhibits remarkable polyethylene hydrocracking performance, achieving approximately 90% conversion and higher liquid fuel selectivity. The complementary analysis of multimodal spectroscopy and in-situ imaging techniques advance our fundamental understanding of structure-activity relationships in zeolite-supported noble metal NPs catalysts.

The complex coupling between thermoelectric parameters makes it extremely challenging to improve the performance of materials. Typically, the reduction of thermal conductivity by incorporating porous structures often leads to a compromise in electrical conductivity. Herein, we present high-ion-conductive zeolite X (including Na-, Ca-, and Li-low silica type-X (LSX)) as the subnanoporous additive in the Bi0.4Sb1.6Te3 (BST) matrix. Owing to the high pore charge density of zeolite X, the decrease in conductivity is effectively suppressed while maintaining a low thermal conductivity. Positively charged metal cation (M+) and valence electron of oxygen atom in aluminum-oxide tetrahedron of zeolite X achieve charge balance. Cationic with different electronegativity regulated electrons of oxygen atom transferred from the oxygen atoms to the BST matrix. The lower electronegativity of Na+ leads to a higher electron density surrounding oxygen atoms in Na-LSX. Thus, more electrons are transferred to the BST matrix from the oxygen atoms in Na-LSX and form Teu2013O bonds. Ultimately, the figure-of-merit (ZT) peak of BST/0.8 wt.% Na-LSX nanocomposites reached 1.47 at 373 K, with a huge cooling temperature difference of 69.4 K and an excellent thermoelectric conversion efficiency of 6.95%. This work exploits the stable and unique three-dimensional pore structure of X-type molecular sieves, broadening their potential application in the thermoelectric medium temperature range.