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.

A Universal Approach for Sustainable Urea Synthesis via Intermediate Assembly at the Electrode/Electrolyte Interface.

Electrocatalytic C-N coupling process is indeed a sustainable alternative for direct urea synthesis and co-upgrading of carbon dioxide and nitrate wastes. However, the main challenge lies in the unactivated C-N coupling process. Here, we proposed a strategy of intermediate assembly with alkali metal cations to activate C-N coupling at the electrode/electrolyte interface. Urea synthesis activity follows the trend of Li+

Cu-In Dual Sites with Sulfur Defects Toward Superior Ethanol Electrosynthesis from CO2 Electrolysis.

The electrosynthesis of multi-carbon chemicals from excess CO2 is an area of great interest for research and commercial applications. However, improving both the yield of CO2 -to-ethanol conversion and the stability of the catalyst at the same time is proving to be a challenging issue. Here we propose to stabilize active Cu(I) and In dual sites with sulfur defects through an electro-driven intercalation strategy, which leads to the delocalization of electron density that enhances orbital hybridizations between the Cu-C and In-H bonds. Hence, the energy barrier for the rate-limiting *CHO formation step is reduced toward the key *OCHCHO* formation during ethanol production, which is also facilitated by the combined Cu site enabling C-C coupling and In site with a higher oxygen affinity based on both thermodynamic and kinetic calculations. Accordingly, such dual-site catalyst achieves a high partial current density toward ethanol of 409 ± 15 mA/cm2 for over 120 hours. Furthermore, a scaled-up flow cell is assembled with an industrial-relevant current of 5.7 A for over 36 hours, in which the carbon loss is less than 2.5% and single-pass carbon efficiency is around 19%. This article is protected by copyright. All rights reserved.

Bridging Trans-Scale Electrode Engineering for Mass CO2 Electrolysis.

Electrochemical CO2 upgrade offers an artificial route for carbon recycling and neutralization, while its widespread implementation relies heavily on the simultaneous enhancement of mass transfer and reaction kinetics to achieve industrial conversion rates. Nevertheless, such a multiscale challenge calls for trans-scale electrode engineering. Herein, three scales are highlighted to disclose the key factors of CO2 electrolysis, including triple-phase boundaries, reaction microenvironment, and catalytic surface coordination. Furthermore, the advanced types of electrolyzers with various electrode design strategies are surveyed and compared to guide the system architectures for continuous conversion. We further offer an outlook on challenges and opportunities for the grand-scale application of CO2 electrolysis. Hence, this comprehensive Perspective bridges the gaps between electrode research and CO2 electrolysis practices. It contributes to facilitating the mixed reaction and mass transfer process, ultimately enabling the on-site recycling of CO2 emissions from industrial plants and achieving net negative emissions.

Constructing Nanocaged Enzymes for Synergistic Catalysis of CO2 Reduction.

Promoting the activity of biological enzymes under in vitro environment is a promising technique for bioelectrocatalytic reactions, such as the conversion of carbon dioxide (CO2 ) into valuable chemicals, which is a promising strategy to address the environmental issue of CO2 in the atmosphere; however, this technique remains challenging. Herein, a nanocage structure for enzyme confinement is synthesized to enable the in situ encapsulation of formate dehydrogenase (FDH) in a porous metal-organic framework, which acts as a coenzyme and boosts the hybrid synergistic catalysis using enzymes. This study reveals that the synthesized FDH@ZIF-8 nanocage-structured hybrid (CSH) catalyst exhibits an improved catalytic ability of the enzymes and increases the hydrophobicity of the electrode and its affinity to CO2 . Thus, CSH can trap CO2 and control its microenvironments. The CSH catalyst boosts the conversion rate of CO2 to formic acid (HCOOH) to 28 times higher than that when using pure FDH. The in situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) spectra indicates that OCHO* is the key intermediate. Density functional theory (DFT) calculations show that CSH has extremely low overpotential and is particularly effective for producing formate. This protection architecture for enzymes considerably promotes their biological application under in vitro environments.

Dual-Scale Integration Design of Sn-ZnO Catalyst toward Efficient and Stable CO2 Electroreduction.

Electrochemical CO2 reduction to CO is a potential sustainable strategy for alleviating CO2 emission and producing valuable fuels. In the quest to resolve its current problems of low-energy efficiency and insufficient durability, a dual-scale design strategy is proposed by implanting a non-noble active Sn-ZnO heterointerface inside the nanopores of high-surface-area carbon nanospheres (Sn-ZnO@HC). The metal d-bandwidth tuning of Sn and ZnO alters the extent of substrate-molecule orbital mixing, facilitating the breaking of the *COOH intermediate and the yield of CO. Furthermore, the confinement effect of tailored nanopores results in a beneficial pH distribution in the local environment around the Sn-ZnO nanoparticles and protects them against leaching and aggregating. Through integrating electronic and nanopore-scale control, Sn-ZnO@HC achieves a quite low potential of -0.53 V vs reversible hydrogen electrode (RHE) with 91% Faradaic efficiency for CO and an ultralong stability of 240 h. This work provides proof of concept for the multiscale design of electrocatalysts.

Nano-crumples induced Sn-Bi bimetallic interface pattern with moderate electron bank for highly efficient CO2 electroreduction.

CO2 electroreduction reaction offers an attractive approach to global carbon neutrality. Industrial CO2 electrolysis towards formate requires stepped-up current densities, which is limited by the difficulty of precisely reconciling the competing intermediates (COOH* and HCOO*). Herein, nano-crumples induced Sn-Bi bimetallic interface-rich materials are in situ designed by tailored electrodeposition under CO2 electrolysis conditions, significantly expediting formate production. Compared with Sn-Bi bulk alloy and pure Sn, this Sn-Bi interface pattern delivers optimum upshift of Sn p-band center, accordingly the moderate valence electron depletion, which leads to weakened Sn-C hybridization of competing COOH* and suitable Sn-O hybridization of HCOO*. Superior partial current density up to 140 mA/cm2 for formate is achieved. High Faradaic efficiency (>90%) is maintained at a wide potential window with a durability of 160 h. In this work, we elevate the interface design of highly active and stable materials for efficient CO2 electroreduction.

Hierarchically Nanostructured Solid-State Electrolyte for Flexible Rechargeable Zinc-Air Batteries.

The construction of safe and environmentally-benign solid-state electrolytes (SSEs) with intrinsic hydroxide ion-conduction for flexible zinc-air batteries is highly desirable yet extremely challenging. Herein, hierarchically nanostructured CCNF-PDIL SSEs with reinforced concrete architecture are constructed by nanoconfined polymerization of dual-cation ionic liquid (PDIL, concrete) within a robust three-dimensional porous cationic cellulose nanofiber matrix (CCNF, reinforcing steel), where plenty of penetrating ion-conductive channels are formed and undergo dynamic self-rearrangement under different hydrated levels. The CCNF-PDIL SSEs synchronously exhibit good flexibility, mechanical robustness, superhigh ion conductivity of 286.5 mS cm-1 , and decent water uptake. The resultant flexible solid-state zinc-air batteries deliver a high-power density of 135 mW cm-2 , a specific capacity of 775 mAh g-1 and an ultralong cycling stability with continuous operation of 240 hours for 720 cycles, far outperforming those of the state-of-the-art solid-state batteries. The marriage of biomaterials with the diversity of ionic liquids creates enormous opportunities to construct advanced SSEs for solid-state batteries.

Porous organic polymers for Li-chemistry-based batteries: functionalities and characterization studies.

Porous organic polymers (POPs), a versatile class of materials that possess many tunable properties such as high chemical absorptivity and ionic conductivity, are emerging candidate electrode materials, permselective membranes, ionic conductors, interfacial stabilizers and functional precursors to synthesize advanced porous carbon. Based on their crystal structure features, the emerging POPs can be classified into two subclasses: amorphous POPs (hyper cross-linked polymers, polymers with intrinsic microporosity, conjugated microporous polymers, porous aromatic frameworks, etc.) and crystalline POPs (covalent organic frameworks, etc.). This tutorial review provides a brief introduction of different types of POPs in terms of their classification and functions for tackling the remaining challenges in various types of Li-chemistry-based batteries. In situ and ex situ characterization studies are also discussed to highlight their importance and applicability for the structural investigation of POPs to reveal the underlying mechanism of POPs over the course of the electrochemical process. Although some revolutionary advances have been achieved, the development of POPs in Li-chemistry-based batteries is still in its infancy. Perspectives regarding future application and mechanistic insights of POPs in battery studies are outlined at the end.

Emerging Trends in Sustainable CO2 -Management Materials.

With the rising level of atmospheric CO2 worsening climate change, a promising global movement toward carbon neutrality is forming. Sustainable CO2 management based on carbon capture and utilization (CCU) has garnered considerable interest due to its critical role in resolving emission-control and energy-supply challenges. Here, a comprehensive review is presented that summarizes the state-of-the-art progress in developing promising materials for sustainable CO2 management in terms of not only capture, catalytic conversion (thermochemistry, electrochemistry, photochemistry, and possible combinations), and direct utilization, but also emerging integrated capture and in situ conversion as well as artificial-intelligence-driven smart material study. In particular, insights that span multiple scopes of material research are offered, ranging from mechanistic comprehension of reactions, rational design and precise manipulation of key materials (e.g., carbon nanomaterials, metal-organic frameworks, covalent organic frameworks, zeolites, ionic liquids), to industrial implementation. This review concludes with a summary and new perspectives, especially from multiple aspects of society, which summarizes major difficulties and future potential for implementing advanced materials and technologies in sustainable CO2 management. This work may serve as a guideline and road map for developing CCU material systems, benefiting both scientists and engineers working in this growing and potentially game-changing area.

Bioinspired Tough Solid-State Electrolyte for Flexible Ultralong-Life Zinc-Air Battery.

Manufacturing advanced solid-state electrolytes (SSEs) for flexible rechargeable batteries becomes increasingly important but remains grand challenge. The sophisticated structure of robust animal dermis and good water-retention of plant cell in nature grant germane inspirations for designing high-performance SSEs. Herein, tough bioinspired SSEs with intrinsic hydroxide ion (OH- ) conduction are constructed by in situ formation of OH- conductive ionomer network within a hollow-polymeric-microcapsule-decorated hydrogel polymer network. By virtue of the bioinspired design and dynamic dual-penetrating network structure, the bioinspired SSEs simultaneously obtain mechanical robustness with 1800% stretchability, good water uptake of 107 g g-1 and water retention, and superhigh ion conductivity of 215 mS cm-1 . The nanostructure of bioinspired SSE and related ion-conduction mechanism are revealed and visualized by molecular dynamics simulation, where plenty of compact and superfast ion-transport channels are constructed, contributing to superhigh ion conductivity. As a result, the flexible solid-state zinc-air batteries assembled with bioinspired SSEs witness high power density of 148 mW cm-2 , specific capacity of 758 mAh g-1 and ultralong cycling stability of 320 h as well as outstanding flexibility. The bioinspired methodology and deep insight of ion-conduction mechanism will shed light on the design of advanced SSEs for flexible energy conversion and storage systems.

A Gas-Phase Migration Strategy to Synthesize Atomically Dispersed Mn-N-C Catalysts for Zn-Air Batteries.

Mn and N codoped carbon materials are proposed as one of the most promising catalysts for the oxygen reduction reaction (ORR) but still confront a lot of challenges to replace Pt. Herein, a novel gas-phase migration strategy is developed for the scale synthesis of atomically dispersed Mn and N codoped carbon materials (g-SA-Mn) as highly effective ORR catalysts. Porous zeolitic imidazolate frameworks serve as the appropriate support for the trapping and anchoring of Mn-containing gaseous species and the synchronous high-temperature pyrolysis process results in the generation of atomically dispersed Mn-Nx active sites. Compared to the traditional liquid phase synthesis method, this unique strategy significantly increases the Mn loading and enables homogeneous dispersion of Mn atoms to promote the exposure of Mn-Nx active sites. The developed g-SA-Mn-900 catalyst exhibits excellent ORR performance in the alkaline media, including a high half-wave potential (0.90 V vs reversible hydrogen electrode), satisfactory durability, and good catalytic selectivity. In the practical application, the Zn-air battery assembled with g-SA-Mn-900 catalysts shows high power density and prominent durability during the discharge process, outperforming the commercial Pt/C benchmark. Such a gas-phase synthetic methodology offers an appealing and instructive guide for the logical synthesis of atomically dispersed catalysts.

Electrolyte Design for Lithium Metal Anode-Based Batteries Toward Extreme Temperature Application.

Lithium anode-based batteries (LBs) are highly demanded in society owing to the high theoretical capacity and low reduction potential of metallic lithium. They are expected to see increasing deployment in performance critical areas including electric vehicles, grid storage, space, and sea vehicle operations. Unfortunately, competitive performance cannot be achieved when LBs operating under extreme temperature conditions where the lithium-ion chemistry fail to perform optimally. In this review, a brief overview of the challenges in developing LBs for low temperature (<0 °C) and high temperature (>60 °C) operation are provided followed by electrolyte design strategies involving Li salt modification, solvation structure optimization, additive introduction, and solid-state electrolyte utilization for LBs are introduced. Specifically, the prospects of using lithium metal batteries (LMBs), lithium sulfur (Li-S) batteries, and lithium oxygen (Li-O2 ) batteries for performance under low and high temperature applications are evaluated. These three chemistries are presented as prototypical examples of how the conventional low temperature charge transfer resistances and high temperature side reactions can be overcome. This review also points out the research direction of extreme temperature electrolyte design toward practical applications.

"Two Ships in a Bottle" Design for Zn-Ag-O Catalyst Enabling Selective and Long-Lasting CO2 Electroreduction.

Electrochemical CO2 reduction (CO2RR) using renewable energy sources represents a sustainable means of producing carbon-neutral fuels. Unfortunately, low energy efficiency, poor product selectivity, and rapid deactivation are among the most intractable challenges of CO2RR electrocatalysts. Here, we strategically propose a "two ships in a bottle" design for ternary Zn-Ag-O catalysts, where ZnO and Ag phases are twinned to constitute an individual ultrafine nanoparticle impregnated inside nanopores of an ultrahigh-surface-area carbon matrix. Bimetallic electron configurations are modulated by constructing a Zn-Ag-O interface, where the electron density reconfiguration arising from electron delocalization enhances the stabilization of the *COOH intermediate favorable for CO production, while promoting CO selectivity and suppressing HCOOH generation by altering the rate-limiting step toward a high thermodynamic barrier for forming HCOO*. Moreover, the pore-constriction mechanism restricts the bimetallic particles to nanosized dimensions with abundant Zn-Ag-O heterointerfaces and exposed active sites, meanwhile prohibiting detachment and agglomeration of nanoparticles during CO2RR for enhanced stability. The designed catalysts realize 60.9% energy efficiency and 94.1 ± 4.0% Faradaic efficiency toward CO, together with a remarkable stability over 6 days. Beyond providing a high-performance CO2RR electrocatalyst, this work presents a promising catalyst-design strategy for efficient energy conversion.

Magnetic-Field-Stimulated Efficient Photocatalytic N2 Fixation over Defective BaTiO3 Perovskites.

Efficient coupling solar energy conversion and N2 fixation by photocatalysis has been shown promising potentials. However, the unsatisfied yield rate of NH3 curbs its forward application. Defective typical perovskite, BaTiO3 , shows remarkable activity under an applied magnetic field for photocatalytic N2 fixation with an NH3 yield rate exceeding 1.93 mg L-1 h-1 . Through steered surface spin states and oxygen vacancies, the electromagnetic synergistic effect between the internal electric field and an external magnetic field is stimulated. X-ray absorption spectroscopy and density functional theory calculations reveal the regulation of electronic and magnetic properties through manipulation of oxygen vacancies and inducement of Lorentz force and spin selectivity effect. The electromagnetic effect suppresses the recombination of photoexcited carriers in semiconducting nanomaterials, which acts synergistically to promote N2 adsorption and activation while facilitating fast charge separation under UV-vis irradiation.

Microporous framework membranes for precise molecule/ion separations.

Microporous framework membranes such as metal-organic framework (MOF) membranes and covalent organic framework (COF) membranes are constructed by the controlled growth of small building blocks with large porosity and permanent well-defined micropore structures, which can overcome the ubiquitous tradeoff between membrane permeability and selectivity; they hold great promise for the enormous challenging separations in energy and environment fields. Therefore, microporous framework membranes are endowed with great expectations as next-generation membranes, and have evolved into a booming research field. Numerous novel membrane materials, versatile manipulation strategies of membrane structures, and fascinating applications have erupted in the last five years. First, this review summarizes and categorizes the microporous framework membranes with pore sizes lower than 2 nm based on their chemistry: inorganic microporous framework membranes, organic-inorganic microporous framework membranes, and organic microporous framework membranes, where the chemistry, fabrications, and differences among these membranes have been highlighted. Special attention is paid to the membrane structures and their corresponding modifications, including pore architecture, intercrystalline grain boundary, as well as their diverse control strategies. Then, the separation mechanisms of membranes are covered, such as diffusion-selectivity separation, adsorption-selectivity separation, and synergetic adsorption-diffusion-selectivity separation. Meanwhile, intricate membrane design to realize synergistic separation and some emerging mechanisms are highlighted. Finally, the applications of microporous framework membranes for precise gas separation, liquid molecule separation, and ion sieving are summarized. The remaining challenges and future perspectives in this field are discussed. This timely review may provide genuine guidance on the manipulation of membrane structures and inspire creative designs of novel membranes, promoting the sustainable development and steadily increasing prosperity of this field.

Analogous Mixed Matrix Membranes with Self-Assembled Interface Pathways.

The implementation of mixed matrix membranes (MMMs) for sub-angstrom scale gas separations remains a grand challenge. Herein, a series of analogous mixed matrix membrane (AMMMs) were constructed via molecular-level hybridization by utilizing a reactive ionic liquid (RIL) as the continuous phase and graphene quantum dots (GQD) as nanofiller for sub-angstrom scale ethylene/ethane (0.416 nm/0.443 nm) separation. With a small number of GQDs (3.5 wt%) embedded in GQD/RIL AMMMs, ethylene permeability soared by 3.1-fold, and ethylene/ethane selectivity simultaneously boosted by nearly 60 % and reached up to 99.5, which outperformed most previously reported state-of-the-art membranes. Importantly, the interfacial pathway structure was visualized and their self-assembly mechanism was revealed, where the non-covalent interactions between RIL and GQDs induced the local arrangement of IL chains to self-assemble into plenty of compact and superfast interfacial pathways, contributing to the combination of superhigh permeability and selectivity.

Manipulating Au-CeO2 Interfacial Structure Toward Ultrahigh Mass Activity and Selectivity for CO2 Reduction.

Deploying the application of Au-based catalysts directly on CO2 reduction reactions (CO2 RR) relies on the simultaneous improvement of mass activity (usually lower than 10 mA mg-1 Au at -0.6 V) and selectivity. To achieve this target, we herein manipulate the interface of small-size Au (3.5 nm) and CeO2 nanoparticles through adjusting the surface charge of Au and CeO2 . The well-regulated interfacial structure not only guarantees the utmost utilization of Au, but also enhances the CO2 adsorption. Consequently, the mass activity (CO) of the optimal AuCeO2 /C catalyst reaches 139 mA mg-1 Au with 97 % CO faradaic efficiency (FECO ) at -0.6 V. Moreover, the strong interaction between Au and CeO2 endows the catalyst with excellent long-term stability. This work affords a charge-guided approach to construct the interfacial structure for CO2 RR and beyond.

Ternary Sn-Ti-O Electrocatalyst Boosts the Stability and Energy Efficiency of CO2 Reduction.

Simultaneously improving energy efficiency (EE) and material stability in electrochemical CO2 conversion remains an unsolved challenge. Among a series of ternary Sn-Ti-O electrocatalysts, 3D ordered mesoporous (3DOM) Sn0.3 Ti0.7 O2 achieves a trade-off between active-site exposure and structural stability, demonstrating up to 71.5 % half-cell EE over 200 hours, and a 94.5 % Faradaic efficiency for CO at an overpotential as low as 430 mV. DFT and X-ray absorption fine structure analyses reveal an electron density reconfiguration in the Sn-Ti-O system. A downshift of the orbital band center of Sn and a charge depletion of Ti collectively facilitate the dissociative adsorption of the desired intermediate COOH* for CO formation. It is also beneficial in maintaining a local alkaline environment to suppress H2 and formate formation, and in stabilizing oxygen atoms to prolong durability. These findings provide a new strategy in materials design for efficient CO2 conversion and beyond.

Boron Nitride Membranes with a Distinct Nanoconfinement Effect for Efficient Ethylene/Ethane Separation.

A BN membrane with a distinct nanoconfinement effect toward efficient ethylene/ethane separation is presented. The horizontal and inclined self-assembly of 2D BN nanosheets endow the BN membrane with abundant percolating nanochannels, and these nanochannels are further decorated by reactive ionic liquids (RILs) to tailor their sizes as well as to achieve nanoconfinement effect. The noncovalent interactions between RIL and BN nanosheets favor the ordered alignment of the cations and anions of RIL within BN nanochannels, which contributes to a fast and selective ethylene transport. The resultant membranes exhibit an unprecedented separation performance with superhigh C2 H4 permeance of 138 GPU and C2 H4 /C2 H6 selectivity of 128 as well as remarkably improved long-term stability for 180 h, outperforming reported state-of-the-art membranes.