Traditional nitrate (NO3⁻) synthesis relies on energy-intensive Haber-Bosch and Ostwald processes, whereas photoelectrochemical nitrogen oxidation reaction (PEC NOR) is a green alternative with scarce high-efficiency catalysts. Herein, a synergistic strategy integrating ionic liquid (IL) modification, Z-scheme heterojunction engineering and defect site construction was proposed to tailor the catalyst electronic structure and surface microenvironment for PEC N2-to-NO3⁻ conversion. A sandwich-like IL@FMO/CFO@IL nanoreactor with abundant oxygen vacancies (Ov) and [Fe–O–Cu–Ov] frustrated Lewis pairs was fabricated. As corroborated by experimental and theoretical studies, the hollow dual-confinement structure enriched active sites and the encapsulated IL accelerated triphase interfacial kinetics via hydrophobicity and intermediate stabilization. This configuration enabled full utilization of electrons to drive O2 reduction to ∙OH and simultaneously utilizing holes from the anode to synergistically promote N2 oxidization towards NO3⁻. The IL@FMO/CFO@IL delivered a NO3⁻ production rate of 23.8 μmol h−1 cm−2 with a Faradaic efficiency of 38.4% in a neutral flow cell. A novel vapor-fed PEC cell further directly yield 26.75 mmol L−1 HNO3 from N2, O2 and water vapor without any electrolyte additives or downstream purification. This work enables efficient HNO3 production via rational catalytic reactor design, offering a green, sustainable and energy-saving technological paradigm for N2 fixation.

Electrocatalytic hydrodechlorination (EHDC) is promising for the removal of chlorophenol pollutants from water due to its mild reaction conditions, high efficiency and facile continuous operation. The previously reported low-coordination N-anchored single-atom Pd catalysts show excellent initial activity but suffer from deactivation induced by structural degradation, limiting their industrial applications. To resolve this issue, we proposed a novel strategy to construct a highly active, selective and stable electrocatalyst by implanting single-atom Pd1 sites into FeCl3-catalyzed carbonized covalent triazine framework (CTF)-derived carbon with abundant pyridine N atoms and a large specific surface area. These structural features facilitate the formation of well-defined Pd1-N4 sites via Pd ← N coordination. The Pd1-N4 sites promote the reaction between adsorbed H⁎ species and 2,4-dichlorophenol (2,4-DCP) through the Eley-Rideal mechanism and improve H⁎ utilization, thereby improving the catalytic activity. Furthermore, the Pd1-N4 structure with ultrahigh metal-ligand bond dissociation energy overcomes the structural degradation-induced deactivation issue of the reported single-atom Pd catalyst. This work offers a universal and feasible design paradigm for developing high-performance single-atom electrocatalysts toward sustainable abatement of chlorinated organic pollutants.

All-solid-state sodium batteries are considered a promising technology for large-scale energy storage owing to their intrinsic safety and the natural abundance of sodium resources. Although high ionic conductivity is exhibited by sulfide-based systems such as Na3SbS4, challenges in achieving a balance between ionic transport and electrochemical stability remain. In this study, a synergistic cation-anion co-doping strategy is proposed to overcome the intrinsic trade-off of single-element doping. By using first-principles density functional theory combined with ab initio molecular dynamics, the structural, ionic, and electronic properties of Na3SbS4 co-doped with M6+ (M = W, Mo) and X- (X = F, Cl, Br, I) are systematically investigated. Based on comprehensive analysis, the WCl and WBr co-doped systems are found to exhibit the most balanced performance among all candidates. In these systems, wide electronic band gaps are maintained, ensuring excellent electronic insulation. Simultaneously, competitive room-temperature ionic conductivities, associated with low activation energies, are also achieved. This optimal balance is attributed to co-doping-induced lattice distortions. Through these distortions Na+ migration pathways are reconstructed into highly connected diffusion networks, while structural integrity and electronic stability are preserved. In addition to bulk transport properties, first-principles interface calculations reveal favorable interfacial compatibility between Na metal and WCl/WBr-co-doped Na3SbS4, characterized by stable interfacial adhesion and localized charge redistribution, highlighting their practical applicability in all-solid-state sodium batteries. In contrast, Mo-based and F/I-containing systems are characterized by either narrower band gaps or excessive migration barriers at the current 6% doping concentration. However, improved performance may be exhibited at lower concentrations, which can be attributed to reduced defect interaction and impurity-derived states overlap. Overall, the intrinsic structure-property relationships among lattice distortion, migration dimensionality, and electronic structure in co-doped Na3SbS4 are elucidated in this work. It is demonstrated that synergistic anion-cation co-doping is an effective strategy to achieve concurrent enhancement of ionic conductivity and electrochemical stability. Through these findings, theoretical guidance is provided for the rational design of next-generation high-performance sulfide solid-state electrolytes.

Photoelectrochemical co-synthesis of hydrogen peroxide/iodine (H2O2/I2) offers a sustainable alternative to conventional production methods. Nevertheless, developing an efficient bifunctional catalyst capable of simultaneously driving the cathodic oxygen reduction (ORR) and the anodic iodine oxidation reduction (IOR) remains challenging. Herein, a hollow-spindle Z-scheme Fe2O3/Co3O4 nanoconfined reactor featuring abundant oxygen vacancies and an atomic Fe-O-Co interface was rationally designed as a bifunctional catalyst for energy-efficient paired synthesis. The as-constructed bifunctional, progressively hydrophobic integrated photoelectrode comprising Fe2O3/Co3O4 as the catalytic active center on carbon felt (CF) substrate with polytetrafluoroethylene (PTFE) modification (denoted as Fe2O3/Co3O4/PTFE/CF) efficiently promotes oxygen (O2) adsorption and repels H2O2/I2 products, thereby boosting both ORR and IOR. The assembled photoelectrolyzer with synergistic redox reactions only requires a 0.84 V cell voltage to reach a current density of 15 mA cm-2, which is 1.22 V lower than that of a conventional ORR||oxygen evolution reaction (OER) system. The paired-photoelectrosynthesis strategy delivers ultrahigh yields of H2O2 (17.80 mM h-1) and I2 (1.03 mmol h-1) at 15 mA cm-2 simultaneously. Notably, it achieves direct generation of pure iodine for the first time without any complex separation or purification steps, addressing the long-standing industrial challenges of low extraction efficiency and poor product purity. This work offers a feasible and energy-efficient route for the simultaneous synthesis of high-value-added chemicals.

Scalable synthesis of noble metal single-atom catalysts (SACs) is crucial for practical applications but remains challenging due to the 'scaling-up effect' by spatiotemporal variations of concentration/temperature, leading to poor uniformity and/or metal aggregation. Here, we report a continuous-flow microfluidic strategy for mass production of Pt SACs on hierarchical nitrogen-doped carbon nanocages (Pt1/hNCNC), which fundamentally overcomes this limitation. Combined experiments and theoretical simulations indicate that the microfluidic microreactor efficiently avoids local supersaturation via rapid and uniform mixing. In synergy with micropore trapping and nitrogen anchoring of hNCNC, continuous local adsorption equilibrium is maintained, promoting stable immobilization of isolated atoms while suppressing aggregation. This method achieves scalable synthesis of Pt1/hNCNC SACs with high Pt loading (10 wt%), excellent uniformity, and a nearly 300-fold increase in productivity compared to the batch method. When applied in a proton exchange membrane water electrolyzer, the cathode with an ultralow loading of 20 μgPt cm-2 delivers industrial current densities of 1.0/3.0 A cm-2 at low voltages of 1.66/2.00 V, respectively, and operates stably for over 500 h at 1.0 A cm-2. This microfluidic synthesis is also successfully extended to various noble metals (Pd, Au, Ir, Rh, Ru, and multi-elements) and nitrogen-doped carbons, demonstrating broad generality. This work establishes a practical and scalable paradigm for manufacturing high-performance noble metal SACs with deep insights into the dual-scale cooperation between macroscopic fluid dynamics and microscopic support chemistry, bridging laboratory discovery with industrial application of single-atom catalysis.

Alkaline water electrolysis (AWE) membranes require simultaneous suppression of gas permeation and reduction of ion transport resistance. This paper utilizes polysulfone/sulfonated polysulfone (PSF/SPSF) as the polymer matrix and ZrO2 as the inorganic component to prepare asymmetric composite membranes by controlling the SPSF content and employing a controlled pre-evaporation-non-solvent induced phase separation (NIPS) method. This creates a continuous dense top layer and an internal finger-like porous support layer. The representative sample S10 significantly reduces the maximum pore size while maintaining a high porosity structure, thus achieving synergistic optimization of gas barrier and ion transport: compared to commercial Zirfon, the bubble point pressure is increased by approximately 5 times, and the area resistance is reduced to about 1/3; it exhibits a lower and more stable operating voltage under conditions of 80 degrees C, 30 wt% KOH, and 0.6 A & sdot;cm-2. TG and FT-IR analysis after aging showed no significant degradation, indicating good thermal/chemical stability. The study demonstrates that the coupling of the SPSF component and film-forming process for directional control of pore structure provides a feasible material and structural design path for optimizing the performance of AWE membranes.

Electrochemical glycerol oxidation reaction (GOR) is an attractive alternative reaction to oxygen evolution reaction (OER) of water electrolysis due to the lower oxidation potential and value-added oxidation products. Developing high-efficient bifunctional electrocatalysts toward anodic GOR and cathodic hydrogen evolution reaction (HER) still faces a grand challenge. Herein, we have constructed high-entropy alloy (HEA) nanoparticles supported on hierarchical N-doped carbon nanocages (hNCNC) by a facile and rapid microwave synthesis. The optimal catalyst exhibits excellent performance in the glycerol-assisted water electrolysis, with an ultralow cell voltage of 0.373 V at 10 mA & centerdot;cm-2 and a long-term stability over 50 h with nearly 100% Faradaic efficiency for H2. The superior performance is ascribed to the increased capability of C-C cleavage and anti-poisoning for GOR and the multiple active sites for HER due to the high-entropy effect, as well as high dispersion and enhanced stability of HEA nanoparticles on hNCNC. This study not only demonstrates an effective approach for constructing advanced bifunctional electrocatalysts for GOR and HER, but also provides new ideas for energy-efficient hydrogen generation by glycerol-assisted water electrolysis Current density (mA & centerdot;cm-2) 250 200 150 100 50 10 0 No glycerol 0.6 M glycerol 0.373 V 1.517 V 0.5 1.0 1.5 Voltage (V)

Alkaline hydrogen evolution (HER) performance of Ru catalysts is limited by the high activation energy barriers of water dissociation and the poisoning of active sites by OH* intermediates. Herein, the MoxC nanoclusters with distinct crystalline phases (MoC and Mo2C) are supported on hierarchical N-doped carbon nanocages (hNCNC). Long-range disordered Ru nanoclusters are induced to grow on the MoC nanoclusters due to the presence of Mo vacancies, while crystalline Ru nanoclusters grow on both Mo2C nanoclusters and hNCNC due to fewer defects. The Ru-MoC/hNCNC achieves an ultralow overpotential (@10 mA cm-2) of 20 mV, a high turnover frequency of 21.8 H2 s-1 and robust durability in 1 M KOH, much superior to the counterpart of Ru-Mo2C/hNCNC. The anion-exchange membrane water electrolysis device with Ru-MoC/hNCNC cathode delivers an industrial-scale current of 1 A cm-2 at ≈1.65 V in 1.0 M KOH. The theoretical calculation, together with in situ Raman spectra, reveals that the Ru-MoC heterointerfaces promote the water dissociation kinetics on Mo sites, leading to the detached formation of OH* on MoC and H* on Ru. This spatial decoupling of OH* and H* can mitigate the OH* poisoning of Ru and promote subsequent H2 formation, thereby demonstrating excellent alkaline HER performance.

Needle coke features low cost, high carbon yield, and good electrical conductivity. It is considered a promising precursor for the carbon anode for sodium-ion batteries, but poor structural tunability and inferior performance limit further development. Herein, we report a facile strategy to achieve needle coke-derived hard carbon (NCAPS) with multiscale structures via activation with ammonium persulfate (APS). Systematic characterization revealed that ammonium persulfate activation introduced appropriate oxygen-containing functional groups on the surface of needle coke, while creating a turbostratic microstructure with balanced defect density and mesopores, thereby supplying abundant adsorption sites of Na+ and improving electrochemical performance. Benefiting from its appropriate structure and chemical composition, NCAPS exhibited a reversible capacity of 212.6 mAh g-1 after 200 cycles at 0.2C, which was 37% higher than non-activated needle coke-derived hard carbon, and an excellent rate capability of 195.0 mAh g-1 at 5C. We utilized APS-assisted activation to enable multiscale structural optimization, thereby significantly enhancing Na+ storage kinetics and electrochemical performance. Herein, we provide a mild activation approach for designing a high-performance sodium-ion battery hard carbon anode from a low-cost and highly aromatic precursor.

The increasing demand for grid-scale energy storage has intensified the pursuit of cost-effective sodium-ion batteries. O3-type layered sodium cathode materials, such as NaNi1/3Fe1/3Mn1/3O2, offer high theoretical capacities but suffer from severe structural degradation during deep sodiation/desodiation at high-voltage. This degradation stems from anisotropic volume changes and continuous cathode-electrolyte interphase deterioration. Here, we show that a conformal MXene buffering layer constructed on the cathode surface simultaneously mitigates lattice strain accumulation and passivates the interphase. In situ XRD reveals that the MXene layer promotes highly reversible lattice restoration during cycling, while distribution of relaxation times analysis shows effective suppression of the solid-phase diffusion resistance surge at deep discharge states. Density functional theory calculations further demonstrate that the MXene layer weakens the adsorption of reactive PF5 byproducts from -0.46 eV to -0.26 eV, thereby suppressing electrolyte decomposition. Consequently, the cathode delivers remarkable high-voltage cyclability, retaining 60% capacity after 300 cycles at 1C with a 4.2 V cutoff, far exceeding the 13% retention of the bare counterpart. This work provides an effective chemomechanical interface to enhance the structural and interfacial stability of high-voltage O3-type cathodes for advanced sodium-ion batteries.

Propylene carbonate (PC)-based electrolytes are promising for supercapacitors but suffering from oxidative degradation at high voltage and elevated temperature, severely limiting durability. Here, we report a polycyanoalkane (PCA) additive that significantly enhances the stability of the DMPBF4/PC electrolyte, with DMPBF4 as the organic salt and PC as the solvent, for supercapacitors. PCA acts as a bifunctional agent, simultaneously stabilizing BF4− anions in the bulk electrolyte and forming a protective, nitrogen-rich interphase on the positive electrode through preferential oxidation. This dual mechanism effectively suppresses both anion decomposition and solvent oxidation, leading to improved capacitive performance. Supercapacitors with 2 wt% PCA exhibit near-ideal behavior and significantly reduced leakage current, enabling stable operation up to 3.5 V at room temperature. Impressively, at 3.3 V and 65 °C, the PCA-modified electrolyte retains 80% capacitance after 500 h, a substantial improvement over neat PC electrolytes. Post-mortem analyses confirm the formation of a uniform, cyano-rich interphase with reduced degradation products on the positive electrode. This anion receptor-based strategy, combining solvation control and interphase engineering, provides a promising approach to expand the operational limits of PC-based supercapacitors.

Hard carbon is widely regarded as the most promising anode material for commercializing sodium-ion batteries. However, the successful industrial application of hard carbon requires not only the proper selection of cost-effective precursors but also precise regulation of the structures. This review aims to provide a comprehensive summary of advanced hard carbons by using commercial raw materials as precursors and the corresponding structural engineering strategies for the industrialization process. Specifically, we systematically summarize three representative and industrially feasible precursors-(resins, biomass, and needle coke)-with particular emphasis on their origins, synthesis pathways, structural optimization, and corresponding sodium-ion storage performance. In addition, we discuss the remaining challenges associated with the large-scale deployment of hard carbon and provide perspectives on future directions, including economic efficiency through low-cost precursors, environmentally friendly synthetic routes, and the implementation of recyclable manufacturing technologies. This review is expected to offer clear insights and practical guidance for the rational design and preparation of commercial hard carbon anode materials.

Polyurethane (PU) coatings, extensively used for metal surface protection, face limitations in harsh environments due to their insufficient wear resistance. A novel PU composite coating system, synergistically reinforced with modified molybdenum disulfide (MoS2) and silicon carbide (SiC) nanoparticles, was developed to enhance both corrosion and wear resistance. By modifying MoS2 via the silane coupling agent (KH560)-polydopamine (PDA) cross-linking, a dense network was formed to block corrosive agents, while dispersed SiC nanoparticles optimized stress distribution and reduced surface friction. The composite coating containing 10 wt.% SiC (KPM-10S/PU) demonstrates comprehensive performance, exhibiting 342 times higher impedance compared to the pure PU, 79% reduction in the wear loss volume against 316L steel, and outstanding resistance in HNO3 and salt spray tests. Although 15 wt.% SiC (KPM-15S/PU) achieved the highest initial impedance and the lowest friction coefficient, excessive SiC compromised matrix compatibility, increasing corrosion vulnerability. This work elucidates the corrosion blocking and wear inhibition reinforcement mechanism of MoS2-SiC composite, and provides a scalable strategy for designing multifunctional coatings in demanding environments of marine infrastructure.

Pd catalysts showed considerable activity to the oxygen conversions in metal-air batteries, but developing efficient, durable, and low-cost Pd electrocatalysts remains highly challenging. Herein, a Pd single-atom catalyst (SAC) with in-plane PdNxC4-x (1 ≤ x ≤ 4) moieties was reconstructed at 800 °C (Pd1/hNCNC-800) by heating the counterpart with edge-coordinated PdN2Cl2 single sites formed on hierarchical N-doped carbon nanocages at 70 °C (Pd1/hNCNC-70). In alkaline media, the Pd1/hNCNC-800 catalyzes oxygen reduction (ORR) and oxygen evolution (OER) reactions via dominant four-electron pathways as revealed by electrochemical and in situ Raman spectroscopy characterizations, exhibiting outstanding activities and stabilities. The corresponding zinc-air battery demonstrates a maximum power density of 214.4 mW cm-2, a high specific capacity of 810.7 mAh gZn-1, and a long cycle life over 600 h, significantly outperforming the counterparts of Pd1/hNCNC-70 and mixed Pt/C+RuO2 (commercial). Theoretical calculations reveal that multiple PdNxC4-x moieties collectively boost the ORR/OER processes while efficiently inhibiting the migration of Pd atoms. These findings establish the correlation between coordination structure and ORR/OER performance of Pd SACs, providing guidance to develop advanced catalysts for energy applications.

Capacitive deionization (CDI) technology requires use of porous carbons with high volumetric desalination performance, but such carbons are lacking. Herein, porous carbon with superior desalination capacity on the carbon-volume basis was prepared via treating activated biochar with pulsed H2-containing flow (PHF). Mechanism for effects of the PHF on the volumetric performance was explored. Compared with use of atmospheric-pressure H2-containing flow (AHF), utilization of PHF produced biomass-based carbon with higher volumetric adsorption capacity (VAC) at lower treatment temperature and in a shorter time. This was because the PHF accelerated the reaction between H2 and O-containing groups on carbon surface via helping H2O molecule (reaction product) diffuse out of pores; consequently, average pore size and electrical conductivity of the carbon increased, which promoted ion migration. The porous carbon made by PHF treatment exhibited a VAC of 13.5 mg/cm3 (500 mg/L NaCl solution, 1.2 V), which ranked among the highest value ever reported for carbon materials. Meanwhile, this carbon showed encouraging charge efficiency, long-cycle capacity retention, and average desalination rate (93%, 76.72%, and 0.675 mg/(cm3·min), respectively). This work provided a promising approach for converting biomass into carbon materials with high volumetric desalination efficiency.

The rational design of stable and high-performance adsorbents is crucial for treating complex wastewater. Herein, novel NH2-MXene/MnO2 composites were fabricated via in-situ growth of spherical MnO2 onto amino-functionalized MXene (NH2-MXene). The amino functionalization introduced abundant active groups, while the intercalated MnO2 nanostructure effectively prevented MXene layer restacking, thereby significantly enhancing pollutant adsorption. By optimizing the (3-aminopropyl) triethoxysilane (APTES) dosage, the composite morphology was tuned, with the optimized N8-M/M sample exhibiting a well-defined intercalated architecture. This composite demonstrated excellent adsorption capacities, achieving maximum uptakes of 793.48 mg g(-1) for tetracycline (TC) and 589.89 mg g(-1) for Cr(VI), along with a strong affinity for organic dyes (malachite green and methyl orange). Remarkably, after three months of storage, the composite retained its structural integrity and over 80% of its initial adsorption performance. Beyond conventional kinetic and isotherm analyses, advanced statistical physical modeling (monolayer model with one energy) was employed to quantitatively elucidate the adsorption mechanism. The model revealed that TC molecules (n > 1) were adsorbed in a non-parallel orientation on multiple binding sites per functional group, while Cr(VI) adsorption orientation was temperature-dependent. The calculated adsorption energies (E: 14.9-17.2 kJ mol(-1) for TC; 21.2-24.7 kJ mol(-1) for Cr(VI)) confirmed an endothermic, chemisorption-dominated process, corroborating the pivotal roles of electrostatic interactions, hydrogen bonding, and pi-pi stacking. This work presents a highly stable MXene-based adsorbent with exceptional removal capabilities for antibiotics, heavy metals, and dyes, offering a promising material for water remediation.

The development of highly efficient oxygen evolution reaction (OER) electrocatalysts is essential for the sustainable production of clean hydrogen energy via proton-exchange membrane (PEM) water electrolysis. Ruthenium (Ru)-based catalysts are promising cost-effective alternatives to iridium (Ir)-based catalysts for acidic OER, yet the trade-off between activity and stability hinders their further optimization. Here, we report a metal-organic framework (MOF) precursor-mediated strategy to synthesize the Ru/RuMnMoO2 heterostructure catalyst. X-ray absorption fine structure, electrochemical evaluation, and theoretical calculation results demonstrated that doped Mn stabilized the lattice oxygen, while Mo promoted electron transfer to Ru, thereby suppressing the peroxide-induced Ru leaching. As expected, the Ru/RuMnMoO2 requires only 163 mV of overpotential to achieve 10 mA cmgeo-2 in acidic electrolyte and maintains long-term stability over 3000 h. Cation probe tests and density functional theory (DFT) calculations confirmed that Ru/RuMnMoO2 followed an adsorbate evolution mechanism (AEM). Notably, a PEM electrolyzer using Ru/RuMnMoO2 as the anode can deliver an ampere-level current density of 1.0 A cmgeo-2 at 1.70 V with a low Ru loading (0.59 mgRu cm-2), outperforming the commercial RuO2-based PEM electrolyzer (2.31 V@ 1.14 mgRu cm-2). Moreover, the cell can stably run for 240 h at a high current density of 3 A cmgeo-2, demonstrating its significant practical potential for alleviating the dependence on iridium.

Proton exchange membrane water electrolysis (PEMWE) is critical for renewable energy integration, yet it remains constrained by costly Ir-based oxygen evolution reaction (OER) catalysts and the activity-stability trade-off of Ru-based alternatives, which suffer from lattice oxygen mechanism (LOM)-induced degradation. Herein, we report an Ir and Mn co-doped Ru/RuO2 heterostructure (IM-Ru/RuO2) synthesized via a metal-organic framework sacrificial template strategy. In this structure, trace Ir anchors lattice oxygen to suppress LOM, while Mn donates electrons to lower Ru oxidation state through asymmetric Ru-O-Mn motifs. Benefiting from this synergistic effect, IM-Ru/RuO2 exhibits an overpotential of 182 mV at 10 mA cm-2 and stability over 600 h. In situ differential electrochemical mass spectroscopy, infrared spectroscopy, and theoretical calculations confirm that the OER proceeds predominantly through an enhanced adsorbate evolution mechanism instead of the detrimental LOM pathway. When integrated into a PEMWE device with ultralow noble-metal loadings (0.36 mgRu cm-2 and 0.024 mgIr cm-2), the catalyst delivers 1.640 V at 1 A cm-2, operates stably for 450 h, and enables a hydrogen production cost of US$0.88 kg-1-below the U.S. DOE 2031 targets. This work establishes a versatile electronic and structural engineering strategy for Ru-based catalysts to advance PEMWE toward large-scale renewable hydrogen production.

Electrocatalytic CO2 reduction (CO2RR) to multicarbon (C2+) products is highly attractive to achieve efficient carbon recycling using renewable energies. However, the selectivity of value-added C2+ products on Cu catalysts is often limited by the insufficient coverage of adsorbed CO (*CO) and the competing hydrogen evolution reaction (HER). Herein, we design a tandem catalyst layer (TCL) for flow cells, which is composed of hydrophobic nickel-nitrogen-carbon (Ni-N-C) material and electro-reduced Cu nanosheets to match the CO generation and carbon-carbon coupling process. The CO2RR tests exhibit high partial current density of ∼338 mA cm-2 and impressive Faradaic efficiency of ∼81% for C2+ products. In situ X-ray absorption fine structure and Raman spectroscopy characterizations, together with theoretical calculations, suggest that the Ni-N-C/Cu TCL substantially enriches the local CO concentration, thereby enhancing the *CO coverage on the Cu surface. Theoretical calculations further indicate that this elevated coverage triggers a thermodynamic transition of CO adsorption from face-centered cubic hollow sites to reactive atop sites, which significantly promotes carbon-carbon coupling between atop *CO and gaseous CO(g). Simultaneously, the hydrophobic nature of the TCL inhibits water diffusion, thereby suppressing the competing HER. This study provides an efficient approach for designing high-performance CO2RR tandem catalysts toward C2+ products.