Perovskite in situ exsolution of nanometals holds distinct superiority in engineering metal−oxide heterointerfaces for boosted CO2 electrolysis within solid oxide electrolyzers, yet it remains constrained by sluggish B-site cation diffusion kinetics and structural instability upon exsolution. Here, we demonstrated that pre-depositing various guest precursors (Co, Fe and Ru) on the surface of Sr2Fe1.35Mo0.45Ni0.2O6−δ (SFMN) via freeze-drying could artfully trigger in situ topotactic exsolution of high-density nanoalloys during reduction, and revealed their guest-cation-selective exchanging behaviors with B-site Fe/Ni cations in SFMN, primarily driven by differences in oxygen affinity and exchange energetics between guest and host cations. Notably, guest Co selectively refilled Ni defects while maintaining Fe defects intact, which favored FeNiCo nanoalloy exsolution and oxygen vacancy (Vӧ) formation, resulting in exceptional CO2 electrolysis performance, with a current density of 2.71 A cm−2, a CO Faradaic efficiency of 95.76% at 1.5 V and 850 °C, and a desirable 100-hour stability. Cross-scale evidence revealed that Fe defects and Vӧ in SFMN could modulate B−O covalency, while active Fe sites in FeNiCo nanoalloys upshifted d-band center to accelerate CO2 adsorption and its dissociation to *CO. This study provides in-depth insights into the novel design of advanced perovskites for a broad spectrum of electrochemical devices.

Photoelectrochemical (PEC) water splitting is a promising approach for solar energy conversion, yet its efficiency is often limited by slow carrier transport and sluggish interfacial reactions. Plasmonic nanostructures can enhance PEC performance through hot electron injection and localized photothermal effects, but the dependence of these processes on localized surface plasmon resonance (LSPR) wavelength and tuning behavior in PEC have not been systematically elucidated. Herein, we construct a series of AuNCs/Ta3N5 photoanodes with tunable LSPR resonance to elucidate the interplay between electronic and thermal effects. In situ spectroscopy and electrochemical measurements reveal that hot electron injection gradually weakens as LSPR wavelength redshifts from 650 to 750 nm, whereas photothermal effect correspondingly enhances. Decoupling experiments further demonstrate that, with the redshift of LSPR wavelength, the hot electron contribution decreases from 80% to 14%, whereas the photothermal contribution increases from 20% to 86%. Notably, AuNCs-2 with an LSPR peak around 700 nm provides sufficient hot electron injection to enhance carrier transport while moderate photothermal heating accelerates interfacial reaction kinetic, delivering a photocurrent density of 9.9 mA cm−2 and an ABPE of 2.72%. These findings may provide mechanistic guidance for designing plasmonic photoanodes with optimized electronic-thermal coupling through LSPR wavelength engineering.

Cu-based photocathodes offer unique advantages for photoelectrochemical CO2 reduction (PEC CO2RR) due to their earth abundance, tunable electronic structures and capacity to efficiently produce multi-carbon (C2+) products. However, their practical performance is fundamentally governed by the dynamics of photogenerated charge carriers, whose generation, separation, accumulation, transport, and extraction directly determine both catalytic efficiency and stability. This review examines how carrier behavior governs key reaction steps, evaluates material design strategies for tuning interfacial charge dynamics, and summarizes emerging techniques for probing these dynamics and interfacial transformations in operando. Looking ahead, integrating precise carrier control with stability and selectivity will be critical, requiring deeper insights into the coupling between carrier physics and catalytic function to guide the development of next-generation Cu-based photocathodes for PEC CO2RR.

The discharge of nitrate wastewater has caused severe environmental problems along with accelerated industrialization. Electrocatalytic nitrate reduction reaction (NO3RR) has emerged as a pivotal technology integrating pollution remedy and resource recovery. In this study, palladium is prescreened as the optimal noble metal for doping into the copper lattice via DFT prediction. The carbon nanotubes-supported intermetallic CuPd (CuPd-CNTs) nanocrystals (mean size 10.78 ± 1.72 nm) are synthesized through a one-step hot-injection method. Pd-doping optimizes the catalytic process by regulating intermediate adsorption behavior and electronic structure, and CNTs effectively inhibit metal oxidation and enhance electron transfer efficiency. Electrochemical measurements demonstrate that CuPd-CNTs exhibit excellent NO3RR performance with low onset potential, Tafel slope, and charge transfer resistance, achieving a high Faradaic efficiency of ∼95% for NH3 production with good stability. In situ FTIR and Raman spectroscopy combined with differential electrochemical mass spectrometry clarify that the critical reaction pathway goes through the first hydrogenation step from *NO to *NOH. Notably, an aluminum-nitrate galvanic system using CuPd-CNTs achieves an open-circuit potential of 1.209 V and a peak power density of 5.46 mW cm-2, and exhibits excellent operational stability, realizing the synergy of nitrate degradation, ammonia production, electrical energy output, and waste aluminum resource recovery.

Developing a self-sustained catalytic system capable of transforming chemical wastes into useful fuels and chemicals represents a vital step toward sustainable energy conversion. Herein, we design strong metal-support interaction (SMSI) enforced intermetallic Cu3Pt-Cu heterointerface that stabilize Cu0-Cu delta+ active centers by enabling ohmic contact and interfacial charge coupling. The formation of heterointerface of Cu3Pt-Cu and coexistence of Cu0 & horbar;Cu delta+ dual states were directly evidenced by XAFS analysis, where wavelet transform contour plots revealed Cu & horbar;Cu and Cu & horbar;Pt scattering features alongside weak Cu-O features indicative of controlled partial oxidation of the Cu core. The stabilized Cu0 & horbar;Cu delta+ interfaces facilitate gem-diol mediated furfural oxidation and selective nitrate reduction by bidirectional H* regulation. The "Furfural-Nitrate" coupled self-powered galvanic cell was efficiently actuated by Cu3Pt-Cu/CF bifunctional catalyst. The constructed cell achieves a near-theoretical open-circuit voltage of similar to 0.76 V and record peak power density (19.31 mW cm-2) while producing NH3 (FE 59.9%), H2 (FE 72.1%), and furoic acid (FE 79.5%), yielding 12.13 kWh kg-1 electricity. This work establishes a strategy to tune interfacial electronic interactions via SMSI for kinetic-promoted electrocatalysis, achieving a benchmark for the innovative hydrogen-ammonia co-production system with simultaneous electricity generation.

Indium (In)-based catalysts hold great promise for the electrochemical CO2 reduction reaction (CO2RR) toward HCOOH formation, yet the lack of precise p-band control and structural instability under industrial current densities severely limit their selectivity and durability. Here, we break ground by designing a series of La1-xSryInO3 perovskites that exhibit electronic tunability and lattice robustness, achieved through smart A-site modulation. Integrated cross-scale analyses revealed that La0.8Sr0.1InO3, engineered via an optimally balanced coregulation of A-site La-deficiency and Sr-doping, most effectively promoted oxygen vacancy formation and electron enrichment at the In-site. This dual effect upshifted the In 5p-band center toward the Fermi Level and enhanced In-O bond covalency through stronger hybridization between In 5p and O 2p orbitals. The elevated p-band center weakened *CO2 adsorption while stabilizing *OCHO intermediates, thereby accelerating rate-determining *CO2 protonation, while the reinforced In-O covalency strengthened the bonding framework, bolstering structural integrity of the In-O lattice. As a result, La0.8Sr0.1InO3 achieved a maximum HCOOH Faradaic efficiency (FEHCOOH) of 92.49% at 300 mA cm(-2), and even at 500 mA cm(-2), it still retained an FEHCOOH of 91.93%, whereas LaInO3 and In2O3 dropped dramatically to 74.32% and 59.35%, respectively. Moreover, during a 48 h stability test, La0.8Sr0.1InO3 maintained a steady potential of -2.01 +/- 0.17 V while preserving its perovskite structure, with FEHCOOH stabilizing at 91.17 +/- 1.90%. This study provides a universal design paradigm via smart A-site modulation for advanced perovskite-based catalysts.

Facing the growing demand for clean and efficient energy conversion, this study presents the first full-spectrum SOEC hybrid system that co-produces heat and hydrogen by integrating a photoresponsive electrode. The electrode is directly irradiated to generate an additional photocurrent, thereby boosting hydrogen yield, while spectral splitting technology simultaneously supplies the SOEC with both heat and electricity. A comprehensive modeling framework, including the SOEC, balance of plant, and solar photoresponsive models, is developed to evaluate system energy and water flow and to analyze factor interactions within the photoresponsive material. Under optimized conditions, the system achieves an exergy efficiency of 58.98%, a solar-to-hydrogen (STH) efficiency of 28.30%, and a solar-to-thermal (STT) efficiency of 43.78%, offering new theoretical insights and practical design rules for highly efficient, flexible full-spectrum solar hydrogen production.

Constructing metal-oxide heterointerfaces has emerged as an effective strategy for enhancing electrochemical CO2 reduction (ECR) performance. However, most efforts to date have focused on precisely tailoring electroactive metal to modulate the heterointerfacial electronic structure, while largely neglecting the critical role of oxide support. Here we break new ground by immobilizing oleylamine (OAm) ligand with rich -NH2 groups not on Pd nanoparticles (NPs), but on CeO2 nano-waxberries (OAm@CeO2 NWs), followed by the assembly of Pd NPs to yield Pd NPs/OAm@CeO2 NWs. Theoretical calculations reveal that -NH2 groups in OAm modify the local electronic configuration of Ce 4f orbitals in CeO2 NWs, thereby enhancing Pd 4d-Ce 4f orbital hybridization. This benefits electron delocalization from Pd to Pd/OAm@CeO2 heterointerface, causing downshift of Pd d-band center and accelerated CO desorption, as corroborated by in situ spectra that Pd NPs/OAm@CeO2 NWs exhibit maximal ratio of linear-adsorbed *COL with minimal absorption energy. Meanwhile, the hydrogen bond formed between *COOH and -NH2 promotes *COOH stabilization. As a result, Pd NPs/OAm@CeO2 NWs deliver nearly 100% CO selectivity across an ultrawide potential window and exceptional stability exceeding 100 h. This study clearly demonstrates how OAm on CeO2 NWs modulates metal-oxide heterointerface, offering a novel design paradigm for advanced electrocatalysts.

ABSTRACT Developing a self–sustained catalytic system capable of transforming chemical wastes into useful fuels and chemicals represents a vital step toward sustainable energy conversion. Herein, we design strong metal–support interaction (SMSI) enforced intermetallic Cu 3 Pt‐Cu heterointerface that stabilize Cu 0 –Cu δ+ active centers by enabling ohmic contact and interfacial charge coupling. The formation of heterointerface of Cu 3 Pt‐Cu and coexistence of Cu 0 ─Cu δ+ dual states were directly evidenced by XAFS analysis, where wavelet transform contour plots revealed Cu─Cu and Cu─Pt scattering features alongside weak Cu–O features indicative of controlled partial oxidation of the Cu core. The stabilized Cu 0 ─Cu δ+ interfaces facilitate gem–diol mediated furfural oxidation and selective nitrate reduction by bidirectional H * regulation. The “Furfural–Nitrate” coupled self–powered galvanic cell was efficiently actuated by Cu 3 Pt‐Cu/CF bifunctional catalyst. The constructed cell achieves a near–theoretical open–circuit voltage of ∼0.76 V and record peak power density (19.31 mW cm −2 ) while producing NH 3 (FE 59.9%), H 2 (FE 72.1%), and furoic acid (FE 79.5%), yielding 12.13 kWh kg −1 electricity. This work establishes a strategy to tune interfacial electronic interactions via SMSI for kinetic–promoted electrocatalysis, achieving a benchmark for the innovative hydrogen–ammonia co–production system with simultaneous electricity generation.

Sr2Fe1.Mo-5(0).O-5(6) (SFM) has drawn attention in SOEC for its favorable ionic and electronic conductivity, yet its CO2 electrolysis performance is limited by A-site Sr segregation and insufficient catalytic activity. In this study, we put forward a solution strategy via the B-O covalent hybridization and spin state regulations through Ga doping. The findings indicate that the Sr segregation resistance and catalytic activity are synergistically optimized. The performance of the single cell employing SFMGa0.25 as cathode can attain 2.11 A & centerdot;cm(-)(2) at 800 degrees C and 1.5 V, signifying a 41% enhancement. Simultaneously, the long-term stability is substantially improved, which can operate stably for over 220 h even under 0.8 A & centerdot;cm(-2). Electronic structure characterizations reveal that the incorporation of Ga strengthens the covalent hybridization between Fe-3d and O-2p, and shifts the Fe 3d and O 2p band centers closer to the Fermi level, which notably promotes the formation of oxygen vacancies as well as the electronic and oxygen ion conductivity. Moreover, Ga doping also increases the proportion of high-spin (HS) Fe4+ species and vacant e(g) orbitals, facilitating the adsorption and reducibility of CO2 molecule. Therefore, this study would offer a novel perspective for the rational design of high-performance SOEC cathode materials in the future.

Metal in situ exsolution endows perovskites with highly active and strongly anchored catalytic sites for high-temperature CO2 electrolysis. However, the concomitant lattice oxygen loss and B-site cation reduction often trigger detrimental phase transitions that compromise long-term durability. Here we demonstrate a chemically non-invasive thermal pre-stabilization strategy that fundamentally resolves this activity-stability trade-off. By elevating the calcination temperature of the double perovskite (DP) Sr1.95Ce0.05Fe1.3Ni0.2Mo0.5O6−δ (SCFNM) from 1100 to 1250 °C, we induce lattice contraction and enhanced BO6 octahedral ordering, which increase B-site cation oxidation states and metal-oxygen bond strength. This robust structure effectively suppresses the DP phase of perovskite transitioning to Ruddlesden-Popper phase during in situ exsolution, while preserving uniformly exsolved NiFe nanoalloys and retaining a higher oxygen vacancy concentration and a stronger CO2 adsorption capacity. As a result, the phase-pre-stabilized NiFe@SCFNM-1250 achieved a current density of 1.72Acm2, a maximum CO Faraday efficiency of 98.63% at 1.5V and 850 °C and a markedly reduced degradation rate of 2.06mAcm–2 h–1 over 100h, which outperforming its non-stabilized counterpart by nearly twofold in durability. This work establishes thermal pre-stabilization as a universally applicable paradigm for balancing catalytic activity with structural stability in perovskite-based electrodes, offering a chemical-doping-free route toward durable CO2 electrolysis.

Cuprous oxide (Cu2O) is a promising photocathode material for photoelectrochemical CO2 reduction (PEC CO2RR) owing to its narrow bandgap and intrinsic catalytic activity. However, its practical application is severely hindered by photocorrosion under illumination, which limits the photostability and performance. To address this, a novel strategy to replace Cu2O entirely with a semiconducting Cu-based metal-organic framework (MOF) was proposed. The low-coordinated Cu+ centers, structural defects, anchoring on reduced graphene oxide (rGO), and TiO2 endow the MOF with enhanced conductivity and visible-light response. The fabricated Cu(I)-Trimesic acid (BTC)@rGO/TiO2 shows high CO Faradaic efficiency and much better photostability over 24 h compared with Cu2O. This work offers anew strategy to engineer stable, active MOF-based photocathodes for CO2 conversion. (c) 2026 The Authors. Published by Published by Elsevier B.V. and Science Press on behalf of Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

The role of the localized surface plasmon resonance (LSPR) effect in promoting the efficiency of hydrogen production by enhancing the catalytic performance has been much studied, but it is a complex physical phenomenon involving electromagnetic and temperature fields, and little research has been conducted on the aspect of its effect on mass transfer. In this study, we investigate the kinetics of individual hydrogen bubble formation during the hydrogen evolution reaction (HER) under LSPR excitation on a microelectrode. Our results reveal a dramatic reduction in the bubble growth-to-detachment time, from 60 s to 0.9 s, accompanied by a two-orders-of-magnitude increase in the hydrogen generation rate. LSPR induced by Au nanoparticles (AuNPs) generates a thermal Marangoni flow at bubble interface, producing a detachment force of 59.10 μN, thereby improving mass transport and reaction efficiency. Increasing light intensity further optimizes mass transfer by shifting the reaction-control regime. These results highlight the multifunctional role of LSPR in enhancing both catalytic and mass-transfer processes in electrochemical hydrogen production, which has implications for LSPR-based photoelectrochemical (PEC) catalysis, electrochemical water splitting, and even CO2 reduction.

ABSTRACT Metallic interatomic spacing emerges as a key activity descriptor in electrocatalysis, yet achieving angstrom‐level precision in its dynamic modulation and establishing definitive structure–activity correlations persist as critical bottlenecks. Here, we developed a phase‐controlled strategy enabling continuous interatomic spacing modulation in a library of hexagonal Pd‐Te nanoplates (NPs), where various atomically ordered intermetallic phases from cubic Pd 4 Te to rhombohedral Pd 20 Te 7 /Pd 8 Te 3 and hexagonal PdTe 2 were synthesized, realizing precise tuning of adjacent Pd‐Pd distances (d Pd‐a‐Pd ) from 2.75 to 4.07 Å. The proof‐of‐concept electrochemical CO 2 reduction (ECR) for CO formation displayed a volcano‐shaped dependence on d Pd‐a‐Pd , where Pd 20 Te 7 NPs with a d Pd‐a‐Pd of 2.88 Å exhibited a maximal CO Faraday efficiency (FE CO ) of 99.9%, and preserved FE CO over 90% at ∼120 mA cm −2 during long‐term stability. Integrated in situ spectra and theoretical calculations confirmed the dominated distance effect over electronic effect, and revealed that increasing d Pd‐a‐Pd upshifted d ‐band center toward the Fermi level while altering *CO adsorption configuration from strongly bound *CO T to weakly bound *CO L , resulting in exceptional ECR activity and CO anti‐poisoning capacity on Pd 20 Te 7 NPs owing to the optimally balanced *COOH adsorption and *CO desorption. This study underscores the pivotal role of interatomic spacing in regulating intermediate adsorption configurations for electrocatalysis.

The electrooxidation of biomass-derived glycerol provides a sustainable pathway for co-producing hydrogen and value-added chemicals, yet its efficiency is critically hindered by the competitive adsorption of reactants and the parasitic oxygen evolution (OER) at high potentials. Here, we propose an active-site decoupling strategy via fluorine doping in spinel CuCo2O4 (CuCo2O4-F) to simultaneously enhance glycerol electrooxidation and suppress OER. The introduced fluorine atoms reconfigure the electronic structure and induce spatial segregation of active sites, thereby OH− preferentially adsorbs on Co centers while glycerol binds to Cu sites. This cooperative adsorption accelerates glycerol oxidation kinetics and switches the OER pathway from a facile lattice oxygen mechanism (LOM) to a sluggish adsorbate evolution mechanism (AEM), thus effectively mitigating parasitic OER. The optimized CuCo2O4-F electrocatalyst achieves a record-high Faradaic efficiency (>90

Hydrogen production using protonic ceramic electrolysis cells (PCECs) is hindered by sluggish oxygen electrode kinetics. Unlike complex material modification strategies, a simpler approach to enhancing electrode performance is highly desirable. Herein, a direct illumination strategy that triggers a vacancy-assisted steam activation mechanism is reported via directly illuminating a classical BSCF (Ba0.5Sr0.5Co0.8Fe0.2O3-δ) anode. Under 5 sun illumination at 650 °C and 1.6 V, an absolute photocurrent of 148.23 mA·cm−2 is achieved, with the highest photocurrent percentage of 31.80% obtained at 1.1 V. Notably, the activation energy for charge transfer decreases from 0.66 eV (dark) to 0.38 eV under illumination, a reduction of 42.42%. In situ X-ray photoelectron spectroscopy confirms that light promotes lattice oxygen release and the partial reduction of B-site transition metal ions (Fe4+ to Fe3+). This work establishes a synergistic photo-electro-thermal mechanism for efficient hydrogen production, opening a new pathway for directly harnessing solar energy in PCEC systems.

Proton exchange membrane (PEM) water electrolysis has emerged as the most promising technology for sustainable hydrogen production, enabling the decarbonization of energy systems and hard-to-abate industrial sectors. This comprehensive review critically examines recent breakthroughs and persistent challenges across the entire PEMWE value chain, from advanced materials to system integration and large-scale deployment. We present a detailed analysis of cutting-edge developments in electrocatalysts, including atomically dispersed Ir/Ru oxides, high-entropy alloys, and non-precious metal alternatives that achieve superior activity and stability while reducing noble metal loadings to ≤ 0.1 mg cm−2. This study systematically evaluates advanced membrane innovations, including ultrathin reinforced perfluorosulfonic acid (PFSA) and hydrocarbon-based alternatives, which achieve simultaneous high proton conductivity and exceptional mechanical durability. A special focus is placed on engineering solutions for porous transport layers and bipolar plates that address critical mass transport limitations at high current densities (≥ 3.0 A cm−2). Beyond component-level advances, we analyse system integration strategies, including dynamic operation (0–200 % rated power), hybrid renewable energy coupling, and high-pressure electrolysis (up to 100 bar), that enhance efficiency and economic viability. We provide a critical assessment of key technological barriers, including membrane degradation mechanisms, catalyst dissolution pathways, and the iridium supply chain crisis, while proposing mitigation strategies through advanced manufacturing and alternative approaches. By integrating fundamental research with industrial perspectives, we present a deployment roadmap that underscores the essential interplay of materials innovation, policy frameworks, and market mechanisms to unlock PEMWE’s potential for the global energy transition.

The photoelectrochemical CO2 reduction reaction (PEC CO2RR) to syngas is of great significance for meeting the needs of the green chemical industry, and controlling the CO/H2 ratio is an important issue. However, the reliance on thin-film semiconductor photocathodes significantly limits the available fabrication methods, and some of the proposed schemes have not been able to precisely tune the CO/H2 ratio by indirectly regulating the electronic structure of active sites. In order to overcome the limitations of traditional fabrication methods, this work proposes a simple photodeposition method for loading Cu2-xTe onto 1% S-doped ZnTe/ZnO to regulate the oxidation state of Cu between +1 and +2 by precisely controlling the deposition light wavelength from violet to red. With shorter deposition light wavelengths, the photon energy increases, leading to a reduced valence state of Cu. As the Cu oxidation state decreases, the band structure of Cu2-xTe-ZnTe can be modulated, with the overall d-band center shifting toward the Fermi level. Besides, the electron density around the Cu active sites increases due to the shorter Cu-Cu bond, resulting in stabilized reaction intermediates and a faster charge transfer process, leading to higher CO selectivity with suppressed hydrogen evolution reaction. As a result, Cu@S-ZnTe/ZnO shows a tunable CO/H2 molar ratio ranging from 0.45 to 1.70 by adjusting the oxidation state of Cu, which can be precisely controlled by simply varying the deposition light wavelength with a specific filter. This demonstrates the great potential of the proposed photodeposition method and the resulting photoelectrocatalyst for practical PEC CO2RR applications.

Single-atom alloys (SAAs) emerge as an intriguing model system for electrocatalysis by combining the advantages of single-atom catalysts and nanoalloys, yet it faces the challenge in engineering their surface structure at the atomic level. Herein, to fully utilize active Pt sites to boost ethanol oxidation electrocatalysis, single-Pt-atoms anchored onto the surface of intermetallic Pd5Bi3 core-ultrathin Pd shell octahedrons, namely a tensile-strained PdPt1 SAA skin, were rationally designed and engineered. This unique PdPt1 SAA skin achieves a record-high mass activity (553.58 A mgPt -1 or 34.73 A mgPt+Pd -1) and outstanding durability toward ethanol oxidation in alkaline electrolyte, outperforming the current high-performance electrocatalysts. Density functional theory (DFT) calculations reveal that the isolated-Pt-atoms effectively enhance the adsorption of ethanol, accelerate the C2 pathway, and enhance the C-C bond cleavage of the *CH2CO intermediate. The wet-chemical fabrication of SAA skin opens up a general strategy to construct model surface that completely exposes and stabilizes active atoms, facilitating the development of highly efficient electrocatalysts.

Perovskite (ABO3)-based cathodes have garnered significant interest for solid-state CO2 electrolysis at elevated temperatures, where B-site cations serve as active centers while A-site cations are traditionally viewed as structural stabilizers. However, tailoring the type and number of A-site cations also exerts a profound influence on oxygen vacancy (Vo) formation behavior and electronic structure of host perovskite. Despite growing recognition of this effect, the precise roles of A-site disorder in modulating the corner-sharing BO6 octahedra, intrinsic properties and catalytic activity of perovskites, and the establishment of a robust correlation between Asite disorder degree and catalytic activity still remain challenging. Herein we engineered a series of perovskites with tunable A-site disorder, and established a quantitative, nonlinear relationship between A-site disorder level (x) and CO2 electrolysis activity (y): y = log6.76(x) + 1.25. The optimal multi-cation-doped La0.2Sr0.2Pr0.2Sm0.2Ba0.2Fe0.8Ni0.2O3_ delta (LSPSBFN) with a disorder degree of 1.61 R delivered a record current density of 2.09 A cm_ 2 at 850 degrees C and 1.5 V for CO2 electrolysis, together with a notably high Faraday efficiency of 97.67% and a superior stability of 120 h, surpassing its lower-disorder counterparts and most benchmark cathodes. Multiscale experiments and DFT calculations revealed that driven by an upward shift of O 2p-band center toward the Fermi level, and strengthened Fe 3d-O 2p orbital hybridization, increasing A-site disorder lowered Vo formation energy, and promoted CO2 adsorption and activation. The logarithmic scaling with diminishing returns at excessive disorder provides a valuable design paradigm for next-generation perovskitebased electrocatalysts.