Selective and Scalable CO2 Electrolysis Enabled by Conductive Zinc Ion-Implanted Zeolite-Supported Cadmium Oxide Nanoclusters.

Catalyst supports play an essential role in catalytic reactions, hinting at pronounced metal-support effects. Zeolites are a propitious support in heterogeneous catalysts, while their use in the electrocatalytic CO2 reduction reaction has been limited as yet because of their electrically insulating nature and serious competing hydrogen evolution reaction (HER). Enlightened by theoretical prediction, herein, we implant zinc ions into the structural skeleton of a zeolite Y to strategically tailor a favorable electrocatalytic platform with remarkably enhanced electronic conduction and strong HER inhibition capability, which incorporates ultrafine cadmium oxide nanoclusters as guest species into the supercages of the tailored 12-ring window framework. The metal d-bandwidth tuning of cadmium by skeletal zinc steers the extent of substrate-molecule orbital mixing, enhancing the stabilization of the key intermediate *COOH while weakening the CO poisoning effect. Furthermore, the strong cadmium-zinc interplay causes a considerable thermodynamic barrier for water dissociation in the conversion of H+ to *H, potently suppressing the competing HER. Therefore, we achieve an industrial-level partial current density of 335 mA cm-2 and remarkable Faradaic efficiency of 97.1% for CO production and stably maintain Faradaic efficiency above 90% at the industrially relevant current density for over 120 h. This work provides a proof of concept of tailored conductive zeolite as a favorable electrocatalytic support for industrial-level CO2 electrolysis and will significantly enhance the adaptability of conductive zeolite-based electrocatalysts in a variety of electrocatalysis and energy conversion applications.

Ni3C/Ni3S2 Heterojunction Electrocatalyst for Efficient Methanol Oxidation via Dual Anion Co-modulation Strategy.

Enhancing active states on the catalyst surface by modulating the adsorption-desorption properties of reactant species is crucial to optimizing the electrocatalytic activity of transition metal-based nanostructured materials. In this work, an efficient optimization strategy is proposed by co-modulating the dual anions (C and S) in Ni3C/Ni3S2, the heterostructured electrocatalyst, which is prepared via a simple hot-injection method. The presence of Ni3C/Ni3S2 heterojunctions accelerates the charge carrier transfer and promotes the generation of active sites, enabling the heterostructured electrocatalyst to achieve current densities of 10/100 mA cm-2 at 1.37 V/1.53 V. The Faradaic efficiencies for formate production coupled with hydrogen evolution approach 100%, accompanied with a stability record of 350 h. Additionally, operando electrochemical impedance spectroscopy (EIS), in situ Raman spectroscopy, and density functional theory (DFT) calculations further demonstrate that the creation of Ni3C/Ni3S2 heterointerfaces originating from dual anions' (C and S) differentiation is effective in adjusting the d-band center of active Ni atoms, promoting the generation of active sites, as well as optimizing the adsorption and desorption of reaction intermediates. This dual anions co-modulation strategy to stable heterostructure provides a general route for constructing high-performance transition metal-based electrocatalysts.

Amorphous K-Co-Mo-Sx Chalcogel: A Synergy of Surface Sorption and Ion-Exchange.

Chalcogel represents a unique class of meso- to macroporous nanomaterials that offer applications in energy and environmental pursuits. Here, the synthesis of an ion-exchangeable amorphous chalcogel using a nominal composition of K2CoMo2S10 (KCMS) at room temperature is reported. Synchrotron X-ray pair distribution function (PDF), X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) reveal a plausible local structure of KCMS gel consisting of Mo5+ 2 and Mo4+ 3 clusters in the vicinity of di/polysulfides which are covalently linked by Co2+ ions. The ionically bound K+ ions remain in the percolating pores of the Co-Mo-S covalent network. XANES of Co K-edge shows multiple electronic transitions, including quadrupole (1s→3d), shakedown (1s→4p + MLCT), and dipole allowed 1s→4p transitions. Remarkably, despite a lack of regular channels as in some crystalline solids, the amorphous KCMS gel shows ion-exchange properties with UO2 2+ ions. Additionally, it also presents surface sorption via [S∙∙∙∙UO2 2+] covalent interactions. Overall, this study underscores the synthesis of quaternary chalcogels incorporating alkali metals and their potential to advance separation science for cations and oxo-cationic species by integrating a synergy of surface sorption and ion-exchange.

Analysis of microscopy techniques to measure segregation in continuous-cast steel slabs.

The accurate characterisation of centreline segregation requires precise measurements of composition variations over large length scales (10 - 1 $^{-1}$ m ${\rm {m}}$ ) across the centreline of the cast product, while having high resolution, sufficient to quantify the significant composition variations between dendrites due to microsegregation at very small length scales (10 - 5 m $^{-5}{\rm {m}}$ ). This study investigates the potential of a novel microscopy technique, named Synchrotron Micro X-ray Flurorescence (SMXRF), to generate large-scale high-resolution segregation maps from a steel sample taken from a thin slab caster. Two methods, Point Analysis and Regression Analysis, are proposed for SMXRF data calibration. By comparing with the traditional Laser-Induced Breakdown Spectroscopy (LIBS), and Electron Probe Micro Analyser (EPMA) techniques, we show that SMXRF is successful in quantitative characterisation of centreline segregation. Over large areas (e.g. 12 × $\times$ 16 mm 2 ${\rm {mm}}^2$ ) and at high resolution (10-50 µ m $\mu\text{m}$ pixel size) various techniques yield comparable outcomes in terms of composition maps and solute profiles. The findings also highlight the importance of both high spatial resolution and large field of view to have a quantitative, accurate, and efficient measurement tool to investigate segregation phenomena.

Molybdenum-Oxysulfide-Functionalized MgAl-Layered Double Hydroxides─A Sorbent for Selenium Oxoanions.

Effective removal of chemically toxic selenium oxoanions at high-capacity and trace levels from contaminated water remains a challenge in current scientific pursuits. Here, we report the functionalization of the MgAl layered double hydroxide with molybdenum-oxysulfide (MoO2S2) anion, referred to as LDH-MoO2S2, and its potential to sequester SeVIO42- and SeIVO32- from aqueous solution. LDH-MoO2S2 nanosheets were synthesized by an ion exchange method in solution. Synchrotron X-ray pair distribution function (PDF) and extended X-ray absorption fine structure (EXAFS) revealed an unexpected transformation of the MoO2S22- to Mo2O2S62- like species during the intercalation process. LDH-MoO2S2 is remarkably efficient in removing SeO42- and SeO32- ions from the ppm to trace level (≤10 ppb), with distribution constant (Kd) ranging from 104 to 105 mL/g. This material showed exceptionally high sorption capacities of 237 and 358 mg/g for SeO42- and SeO32-, respectively. Furthermore, LDH-MoO2S2 demonstrates substantial affinity and efficiency to remove SeO32-/SeO42- even in the presence of competitive ions from contaminated water. Hence, the removal of selenium (VI/IV) oxoanions collectively occurs through reductive precipitation and ion exchange mechanisms. This work provides significant insights into the chemical structure of the MoO2S2 anion into LDH and emphasizes its exceptional potential for high-capacity selenium removal and positioning it as a premier sorbent for selenium oxoanions.

Competitive Coordination Structure Regulation in Deep Eutectic Electrolyte for Stable Zinc Batteries.

Rechargeable zinc-based batteries are finding their niche in energy storage applications where cost, safety, scalability matter, yet they are plagued by rapid performance degradation due to the lack of suitable electrolytes to stabilize Zn anode. Herein, we report a competitive coordination structure to form unique quaternary hydrated eutectic electrolyte with ligand-cation-anion cluster. Unraveled by experiment and calculation results, the competing component can enter initial primary coordination shell of Zn2+ ion, partially substituting Lewis basic eutectic ligands and reinforcing cation-anion interaction. The hydration-deficient complexes induced between competing eutectic as hydrogen bond donor-accepter and water also broaden the electrochemical window and confine free water activity. The altered coordination further leads to robust hybrid organic-inorganic enriched solid electrolyte interphase, enabling passivated surface and suppressed dendrite growth. Noticeably, stable Zn plating/stripping for 8000 cycles with high Coulombic efficiencies of 99.6 % and long cycling life of 10000 cycles for Zn-organic batteries are obtained. Even under harsh conditions (small N/P ratio, low temperature), the profits brought by the competitive eutectic electrolyte are still very prominent. This design principle leveraged by eutectic electrolytes with competitive coordination offers a new approach to improve battery performance.

Integrated "Two-in-One" Strategy for High-Rate Electrocatalytic CO2 Reduction to Formate.

The electrochemical CO2 reduction reaction (ECR) is a promising pathway to producing valuable chemicals and fuels. Despite extensive studies reported, improving CO2 adsorption for local CO2 enrichment or water dissociation to generate sufficient H* is still not enough to achieve industrial-relevant current densities. Herein, we report a "two-in-one" catalyst, defective Bi nanosheets modified by CrOx (Bi-CrOx), to simultaneously promote CO2 adsorption and water dissociation, thereby enhancing the activity and selectivity of ECR to formate. The Bi-CrOx exhibits an excellent Faradic efficiency (≈ 100 %) in a wide potential range from ‒0.4 to ‒0.9 V. In addition, it achieves a remarkable formate partial current density of 687 mA cm‒2 at a moderate potential of ‒0.9 V without iR compensation, the highest value at ‒0.9 V reported so far. Control experiments and theoretical simulations revealed that the defective Bi facilitates CO2 adsorption/activation while the CrOx accounts for enhancing the protonation process via accelerating H2O dissociation. This work presents a pathway to boosting formate production through tuning CO2 and H2O species at the same time.

Phase Transition Engineering of Host Perovskite toward Optimal Exsolution-facilitated Catalysts for Carbon Dioxide Electrolysis.

The in situ exsolution technique of nanoparticles has brought new opportunities for the utilization of perovskite-based catalysts in solid oxide cells. However, the lack of control over the structural evolution of host perovskites during the promotion of exsolution has restricted the architectural exploitation of exsolution-facilitated perovskites. In this study, we strategically broke the long-standing trade-off phenomenon between promoted exsolution and suppressed phase transition via B-site supplement, thus broadening the scope of exsolution-facilitated perovskite materials. Using carbon dioxide electrolysis as an illustrative case study, we demonstrate that the catalytic activity and stability of perovskites with exsolved nanoparticles (P-eNs) can be selectively enhanced by regulating the explicit phase of host perovskites, accentuating the critical role of the architectures of perovskite scaffold in catalytic reactions occurring on P-eNs. The concept demonstrated could potentially pave the way for designing the advanced exsolution-facilitated P-eNs materials and unveiling a wide range of catalytic chemistry taking place on P-eNs.

Photocatalytic disinfection for point-of-use water treatment using Ti3+ self-doping TiO2 nanoparticle decorated ceramic disk filter.

The challenge from pathogenic infections still threatens the health and life of people in developing areas. An efficient, low-cost, and abundant-resource disinfection method is desired for supplying safe drinking water. This study aims to develop a novel Ti3+ doping TiO2 nanoparticle decorated ceramic disk filter (Ti3+/TiO2@CDF) for point-of-use (POU) disinfection of drinking water. The production of Ti3+/TiO2@CDF was optimized to maximize disinfection efficiency and flow rate. Under optimal conditions, the log reduction value (LRV) could reach up to 7.18 and the flaw rate was 108 mL/h. The influences of environmental factors were also investigated. Natural or slightly alkaline conditions, low turbidity, and low concentration of humic acid were favorable for the disinfection of Ti3+/TiO2@CDF, while co-existing HCO3- ions and diatomic cations (Ca2+ and Mg2+) exhibited the opposite effect. Furthermore, the practicability and stability of Ti3+/TiO2@CDF was demonstrated. Ti3+/TiO2@CDF showed high disinfection efficiency for E. coli and S. aureus under a range of concentrations. Long-term experiment indicated that Ti3+/TiO2@CDF was stable. The underlying disinfection mechanisms were investigated and concluded as the combination of retention, adsorption, and photocatalytic disinfection. The developed Ti3+/TiO2@CDF can provide an effective and reliable disinfection tool for POU water treatment in remote area.

Operando Tracking of Solution-Phase Concentration Profiles in Li-Ion Battery Positive Electrodes Using X-ray Fluorescence.

The trade-off between energy density and power capabilities is a challenge for Li-ion battery design as it highly depends on the complex porous structures that holds the liquid electrolyte. Specifically, mass-transport limitations lead to large concentration gradients in the solution-phase and subsequently to crippling overpotentials. The direct study of these solution-phase concentration profiles in Li-ion battery positive electrodes has been elusive, in part because they are shielded by an opaque and paramagnetic matrix. Herein we present a new methodology employing synchrotron hard X-ray fluorescence to observe the concentration gradient formation within Li-ion battery electrodes in operando. This methodology is substantiated with data collected on a model LiFePO4/Li cell using a 1 M LiAsF6 in 1:1 ethylene carbonate/dimethyl carbonate (EC/DMC) electrolyte under galvanostatic and intermittent charge profiles. As such, the technique holds great promise for optimization of new composite electrodes and for numerical model validation.

Sequestration of Selenite and Selenate in Gypsum (CaSO4·2H2O): Insights from the Single-Crystal Electron Paramagnetic Resonance Spectroscopy and Synchrotron X-ray Absorption Spectroscopy Study.

Gypsum is the most common sulfate mineral on Earth's surface and is the dominant solid byproduct in a wide variety of mining and industrial processes, thus representing a major source for heavy metal(loid) contamination, including selenium. Gypsum crystals grown from the gel diffusion technique in 0.02 M Na2SeO4 solution at pH 7.5 and 0.02 M Na2SeO3 solutions at pH 7.5 and 9.0 contain 828, 5198, and 5955 ppm Se, respectively. Synchrotron Se K-edge X-ray absorption spectroscopic analyses show that selenite and selenate are the dominant species in Se4+- and Se6+-doped gypsum, respectively. The single-crystal EPR spectra of Se4+- and Se6+-doped gypsum after gamma-ray irradiation reveal five selenium-centered oxyradicals: SeO2-(I), SeO2-(II), SeO2-(III), SeO3-, and HSeO42-. The former three radicals provide unequivocal evidence for the substitution of their paramagnetic precursor SeO32- for SO42- in the gypsum structure, while the latter two confirm the replacement of SeO42- for SO42-. These results demonstrate that gypsum has a significant capacity for sequestrating both selenite and selenate in the structure but has a marked preference for the former, thus confirming important controls on the mobility and bioavailability of selenium oxyanions and pointing to optimal applications of gypsum for remediating selenium contamination under neutral to alkaline conditions.

Interactive Toxicity of Triclosan and Nano-TiO2 to Green Alga Eremosphaera viridis in Lake Erie: A New Perspective Based on Fourier Transform Infrared Spectromicroscopy and Synchrotron-Based X-ray Fluorescence Imaging.

This study explored the toxicity of triclosan in the presence of TiO2 P25 to the green alga Eremosphaera viridis in Lake Erie. Multiple physicochemical end points were conducted to perform a comprehensive analysis of the toxic effects of individual and combined pollutants. Fourier transform infrared spectromicroscopy and synchrotron-based X-ray fluorescence imaging were first documented to be applied to explore the distribution variation of macromolecules and microelements in single algal cells in interactive toxicity studies. The results were different based on different triclosan concentrations and measurement end points. Comparing with individual pollutants, the toxicity intensified in lipids, proteins, and oxidative stress at 1000 and 4000 µg/L triclosan in the presence of P25. There were increases in dry weight, chlorophyll content, lipids, and catalase content when cells were exposed to P25 and 15.625 µg/L triclosan. The toxicity alleviated when P25 interacted with 62.5 and 250 µg/L triclosan compared with triclosan-only exposure. The reasons could be attributed to the combination of adsorption, biodegradation, and photocatalysis of triclosan by algae and P25, triclosan dispersion by increased biomass, triclosan adherency on algal exudates, and triclosan adsorption site reduction on algae surface owing to P25's taking over. This work provides new insights into the interactive toxicity of nanoparticles and personal care products to freshwater photosynthetic organisms. The findings can help with risk evaluation for predicting outcomes of exposure to mixtures and with prioritizing further studies on joint toxicity.

Effects of Dolomitic Limestone Application on Zinc Speciation in Boreal Forest Smelter-Contaminated Soils.

Anthropogenic activities at the HudBay Minerals, Inc., Flin Flon (Manitoba, Canada) mining and processing facility have severely affected the surrounding boreal forest ecosystem. Soil contamination occurred via a combination of metal and sulfuric acid deposition and has resulted in forest dieback and ineffective natural recovery. A community-led effort to revegetate areas of the landscape through the application of a dolomitic limestone has been met with varied success. Zinc (Zn) speciation has shown to be closely linked to the presence or absence of an invasive metal-tolerant grass species, with soils being broadly classed into two revegetation response groups. Group I, characterized by the absence of metal-tolerant grasses, and group II, characterized by the presence of metal-tolerant grasses. The systematic approach used to lime areas of the landscape produced a liming chronosequence for each group. This study used a combination of X-ray absorption spectroscopy, X-ray fluorescence mapping, and X-ray diffraction techniques to determine the effect of liming on Zn speciation in these chronosequences. Liming group I soils resulted in the formation of a neo-phase Zn-Al-hydroxy interlayer coprecipitate and subsequent rapid boreal forest revegetation. The effect of liming on Zn speciation on the group II soils resulted in a gradual transition of increasingly stable adsorption species, culminating with a stable Zn-Al-layered double hydroxide precipitate. Boreal forest vegetation has failed to recolonize group II soils during the study. However, the formation of the layered double hydroxide species resulted in a significant reduction in CaCl-extractable Zn. Further research is required to determine how to promote the revegetation of these soils.

Characterizing Zinc Speciation in Soils from a Smelter-Affected Boreal Forest Ecosystem.

HudBay Minerals, Inc., has mined and/or processed Zn and Cu ore in Flin Flon, MB, Canada, since the 1930s. The boreal forest ecosystem and soil surrounding these facilities have been severely impacted by mixed metal contamination and HSO deposition. Zinc is one of the most prevalent smelter-derived contaminants and has been identified as a key factor that may be limiting revegetation. Metal toxicity is related to both total concentrations and speciation; therefore, X-ray absorption spectroscopy and X-ray fluorescence mapping were used to characterize Zn speciation in soils throughout the most heavily contaminated areas of the landscape. Zinc speciation was linked to two distinct soil types. Group I soils consist of exposed soils in weathered positions of bedrock outcrops with Zn present primarily as franklinite, a (ZnFeO) spinel mineral. Group II soils are stabilized by an invasive metal-tolerant grass species, with Zn found as a mixture of octahedral (Fe oxides) and tetrahedral Mn oxides) adsorption complexes with a franklinite component. Soil erosion influences Zn speciation through the redistribution of Zn and soil particulates from Group I landscape positions to Group II soils. Despite Group II soils having the highest concentrations of CaCl-extractable Zn, they support metal-tolerant plant growth. The metal-tolerant plants are probably preferentially colonizing these areas due to better soil and nutrient conditions as a result of soil deposition from upslope Group I areas. Zinc concentration and speciation appears to not influence the colonization by metal-tolerant grasses, but the overall soil properties and erosion effects prevent the revegetation by native boreal forest species.

Accelerated Discovery of (TiZrHf)x(NbTa)1- x High-Entropy Alloys With Superior Thermal Stability and a New Crystallization Mechanism.

Nanocrystalline (nc) metals are generally strong yet thermally unstable, rendering them difficult to process and unsuitable for use, particularly at elevated temperatures. Nc multicomponent and high-entropy alloys (HEAs) are found to offer enhanced thermal stability but only in a few empirically discovered systems out of a vast compositional space. In response, this work develops a combinatorial strategy to accelerate the discovery of nc-(TiZrHf)x(NbTa)1- x alloy library with distinct thermal stability, in terms of phases and grain sizes. Based on synchrotron X-ray diffraction and electron microscopy characterizations, a phase transition is observed from amorphous-crystalline nanocomposites to a body-centered cubic (bcc) phase upon annealing. With increased NbTa content (decreased x value), the system tends to achieve thermally stable dual bcc phases upon annealing; in contrast, alloys with increased TiZrHf content (x > 0.6) maintain a single-composition nanocomposite state, impeding crystallization and grain growth. This investigation not only broadens the understanding of thermal stability but also delves into the onset of crystallization in HEA systems.

A new assessment method for water environment safety and its application.

The Three Gorges Reservoir area is recognized by its vast size, dense population, bustling economic and social activities along its banks, and by the significant volume of waterway traffic. These factors make it with a high risk of water pollution accidents, posing a serious threat to water environmental safety. Therefore, it is imperative to conduct a water environmental safety assessment in this region to ensure the safety of the water environment. In the present work, the Driving-Pressure-State-Impact-Response-Risk Water Environmental Safety model was proposed, and a comprehensive water environmental safety assessment system was established. The Water Environment Safety Index was introduced to measure the degree of water environment safety. This model synthesized multiple factors and their interrelationships, enabling a more accurate assessment of water environment safety. By adopting scientifically rigorous evaluation criteria, this assessment method enhanced the reliability and credibility of the results obtained. The water environment safety in the 22 counties and districts of the Three Gorges Reservoir area of Chongqing region from 2017 to 2021 was assessed in terms of temporal changes and spatial differentiation. In general, the overall water environment safety situation in the Three Gorges Reservoir area of Chongqing region is relatively safe, but a few counties/districts (such as Wanzhou District, Jiangjin District, etc.) are still in Warning. Spatially, the water environmental safety condition was relatively better in the northeast compared to the southwest. The main factors threatening water environment safety include: 1) the consequence of the Three Gorges Project, 2) severe soil erosion, 3) industrial, agricultural, and domestic pollution, and 4) frequent water pollution accidents. The present work provided a new method for conducting water environment safety assessments, which is expected to positively contribute to further research in this field.

Prediction and countermeasures of heavy metal copper pollution accident in the Three Gorges Reservoir Area.

In order to mitigate the hazards of water pollution in drinking water source areas (DWSAs), developing applicable models and proposing effective solutions is of paramount significance. The study developed the Heshangshan Drinking Water Source Area (HDWSA) Hydrodynamic Model, integrating Geographic Information System (GIS) into a two-dimensional hydrodynamic water quality model using FORTRAN. TECPLOT360 software (Software Tools for Numerical Simulation with Visualization) visualized contamination transportation and diffusion. The model's relative error is less than 6%, indicating its strong stability and high reliability. The HDWSA in the Three Gorges Reservoir Area (TGRA) was used as a case study, focusing on copper (Cu) as a pollutant. By regulating the flow downstream from the Xiangjiaba Reservoir, Scheduling Group 1 and Scheduling Group 2 respectively increased the flow by 4000 m3/s and 8000 m3/s. The study analyzed the spatio-temporal variations of Cu concentration following pollution accident and flow scheduling. Under accident conditions, it took 71, 61, 49, and 56 min for the Cu concentration in the study area to decrease to below the standard value (1 mg/L) during dry, falling, flood, and storage periods. Scheduling Groups 1 and 2 reduced the pollutant exceedance duration by 19-26 min and 12-18 min across the four water periods.

Polysulfide regulation by defect-modulated Ta3N5-x electrocatalyst toward superior room-temperature sodium-sulfur batteries.

Resolving low sulfur reaction activity and severe polysulfide dissolution remains challenging in metal-sulfur batteries. Motivated by a theoretical prediction, herein, we strategically propose nitrogen-vacancy tantalum nitride (Ta3N5-x) impregnated inside the interconnected nanopores of nitrogen-decorated carbon matrix as a new electrocatalyst for regulating sulfur redox reactions in room-temperature sodium-sulfur batteries. Through a pore-constriction mechanism, the nitrogen vacancies are controllably constructed during the nucleation of Ta3N5-x. The defect manipulation on the local environment enables well-regulated Ta 5d-orbital energy level, not only modulating band structure toward enhanced intrinsic conductivity of Ta-based materials, but also promoting polysulfide stabilization and achieving bifunctional catalytic capability toward completely reversible polysulfide conversion. Moreover, the interconnected continuous Ta3N5-x-in-pore structure facilitates electron and sodium-ion transport and accommodates volume expansion of sulfur species while suppressing their shuttle behavior. Due to these attributes, the as-developed Ta3N5-x-based electrode achieves superior rate capability of 730 mAh g-1 at 3.35 A g-1, long-term cycling stability over 2000 cycles, and high areal capacity over 6 mAh cm-2 under high sulfur loading of 6.2 mg cm-2. This work not only presents a new sulfur electrocatalyst candidate for metal-sulfur batteries, but also sheds light on the controllable material design of defect structure in hopes of inspiring new ideas and directions for future research.

Conductive Zeolite Supported Indium-Tin Alloy Nanoclusters for Selective and Scalable Formic Acid Electrosynthesis.

Upgrading excess CO2 toward the electrosynthesis of formic acid is of significant research and commercial interest. However, simultaneously achieving high selectivity and industrially relevant current densities of CO2-to-formate conversion remains a grand challenge for practical implementations. Here, an electrically conductive zeolite support is strategically designed by implanting Sn ions into the skeleton structure of a zeolite Y, which impregnates ultrasmall In0.2Sn0.8 alloy nanoclusters into the supercages of the tailored 12-ring framework. The prominent electronic and geometric interactions between In0.2Sn0.8 nanoalloy and zeolite support lead to the delocalization of electron density that enhances orbital hybridizations between In active site and *OCHO intermediate. Thus, the energy barrier for the rate-limiting *OCHO formation step is reduced, facilitating the electrocatalytic hydrogenation of CO2 to formic acid. Accordingly, the developed zeolite electrocatalyst achieves an industrial-level partial current density of 322 mA cm-2 and remarkable Faradaic efficiency of 98.2% for formate production and stably maintains Faradaic efficiency above 93% at an industrially relevant current density for over 102 h. This work opens up new opportunities of conductive zeolite-based electrocatalysts for industrial-level formic acid electrosynthesis from CO2 electrolysis and toward practically accessible electrocatalysis and energy conversion.

Interfacial Electronic Modulation of Dual-Monodispersed Pt-Ni3S2 as Efficacious Bi-Functional Electrocatalysts for Concurrent H2 Evolution and Methanol Selective Oxidation.

Constructing the efficacious and applicable bi-functional electrocatalysts and establishing out the mechanisms of organic electro-oxidation by replacing anodic oxygen evolution reaction (OER) are critical to the development of electrochemically-driven technologies for efficient hydrogen production and avoid CO2 emission. Herein, the hetero-nanocrystals between monodispersed Pt (~ 2 nm) and Ni3S2 (~ 9.6 nm) are constructed as active electrocatalysts through interfacial electronic modulation, which exhibit superior bi-functional activities for methanol selective oxidation and H2 generation. The experimental and theoretical studies reveal that the asymmetrical charge distribution at Pt-Ni3S2 could be modulated by the electronic interaction at the interface of dual-monodispersed heterojunctions, which thus promote the adsorption/desorption of the chemical intermediates at the interface. As a result, the selective conversion from CH3OH to formate is accomplished at very low potentials (1.45 V) to attain 100 mA cm-2 with high electronic utilization rate (~ 98%) and without CO2 emission. Meanwhile, the Pt-Ni3S2 can simultaneously exhibit a broad potential window with outstanding stability and large current densities for hydrogen evolution reaction (HER) at the cathode. Further, the excellent bi-functional performance is also indicated in the coupled methanol oxidation reaction (MOR)//HER reactor by only requiring a cell voltage of 1.60 V to achieve a current density of 50 mA cm-2 with good reusability.