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.

Engineering Oxygen Vacancies in In2O3 with Enhanced Polysulfides Immobilization and Selective Catalytic Capability.

Lithium-sulfur (Li-S) battery is identified as an ideal candidate for next-generation energy storage systems in consideration of its high theoretical energy density and abundant sulfur resources. However, the shuttling behavior of soluble polysulfides (LiPSs) and their sluggish reaction kinetics severely limit the practical application of the current Li-S battery. In this work, a series of In2O3 nanocubes with different oxygen vacancy concentrations are designed and prepared via a facile self-template method. The introduced oxygen vacancy on In2O3 can effectively rearrange the charge distribution and enhance sulfiphilic property. Moreover, the In2O3 with high oxygen vacancy concentration (H-In2O3) can slightly slow down the solid-liquid conversion process and significantly accelerate the liquid-solid conversion process, thus reducing the accumulation of LiPSs in electrolyte and inhibiting the shuttle effect. Contributed by the unique selective catalytic capability, the prepared H-In2O3 exhibits excellent electrochemical performance when used as sulfur host. For instance, a high reversible capacity of 609 mAh g-1 is obtained with only 0.044% capacity decay per cycle over 1000 cycles at 1.0 C. This work presents a typical example for designing advanced sulfur hosts, which is crucial for the commercialization of Li-S battery.

Manganese Local Environment Modulation via SiO4 Substitution to Boost Sodium Storage Performance of Na4 MnCr(PO4 )3.

Manganese-based Na superionic conductors (NASICONs) Na4 MnCr(PO4 )3 with three-electron reaction are attractive cathode materials for sodium-ion batteries. However, the irreversible distortion of Mn local structure leads to sluggish electrode kinetics, voltage hysteresis, and poor cycling stability. Here, SiO4 is introduced to substitute PO4 to modulate the local environment of Mn to activate the redox activity and stabilize the reversibility of Na4 MnCr(PO4 )2.9 (SiO4 )0.1 (NMCP-Si). A combined experimental and theoretical investigation have been undertaken to reveal the evolution of electronic structures and Na storage properties associated with SiO4 substitution. The NMCP-Si exhibits much-enhanced rate capability and cycling stability, being attributed to the unique Jahn-Teller distortion (Mn3+ ) that facilitates sodium de/insertion kinetics by optimizing the Na ion diffusion channels. This work addresses the challenge of stabilizing the structure of Mn-based NASICONs and represents a breakthrough in understanding how to improve the Na+ conductivity by regulating local structure.

Understanding the Synthesis Kinetics of Single-Crystal Co-Free Ni-Rich Cathodes.

Non-equilibrium kinetic intermediates are usually preferentially generated instead of thermodynamic stable phases in the solid-state synthesis of layered oxides. Understanding the inherent complexity between thermodynamics and kinetics is important for designing high cationic ordering cathodes. Single-crystal strategy is an effective way to solve the intrinsic chemo-mechanical problems of Ni-rich cathodes. However, the synthesis of high-performance single-crystal is very challenging. Herein, the kinetic reaction path and the formation mechanism of non-equilibrium intermediates in the synthesis of single-crystal Co-free Ni-rich were explored. We demonstrate that the formation of non-equilibrium intermediate and the electrochemical-thermo-mechanical failure can be effectively inhibited by driving low-temperature topotactic lithiation. This work provides a basis for designing high-performance single-crystal Ni-rich layered oxides by regulating the defective structures.

"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.

Developing high safety Li-metal anodes for future high-energy Li-metal batteries: strategies and perspectives.

Developing high-safety Li-metal anodes (LMAs) is extremely important for the application of high-energy Li-metal batteries (LMBs), especially Li-S and Li-O2 battery systems. However, the notorious Li-dendrite growth problem results in serious safety concerns for any energy storage application. Through a recent combination of interface-based science, nanotechnology-based solutions and characterization methods, the LMA is now primed for a technological boom. In this review, the recent emerging strategies and perspectives on LMAs are summarized, following which the current huge evolution in interfacial chemistry regulation, optimizing electrolyte components, designing a rational 'host' for lithium metal, optimizing "solid-state electrolytes" and other emerging strategies for developing high-safety LMAs is highlighted. Furthermore, several state-of-the-art in situ/operando synchrotron-based X-ray techniques for high safety LMB research are introduced. With the further development of LMAs in the future, subsequent application in high energy LMBs is to be expected.

Strain-Modulated Platinum-Palladium Nanowires for Oxygen Reduction Reaction.

Electrocatalytic activity of alloy nanocatalytsts can be manipulated effectively by tuning their physical properties (ensemble, geometric, and ligand effects) to afford optimal surface structure and compositions for proton exchange membrane fuel cell (PEMFC) application. Herein, highly catalytic platinum-palladium nanowires (PtnPd100-n NWs) with a subtle lattice strain and Boerdijk-Coxeter helix type morphology are synthesized through a surfactant-free, thermal single phase solvent method. X-ray diffraction results show that PtnPd100-n NWs are exposed through the (111) facets and their shrinking or expanding lattice parameters can be modulated by the alloy compositions. Electrochemical results reveal that their high catalytic activity correlates with the lattice shrinking, facets, and bimetallic compositions, showing higher activity when the ratio of Pt and Pd is ∼78:22, which is further supported by DFT results. Compared to the nanoparticle type platinum-palladium alloyed catalysts with similar metal compositions (PtnPd100-n NPs), the PtnPd100-n NWs exhibit significantly improved electrocatalytic activity and stability for the oxygen reduction reaction. These findings open new strategies to design the highly active and stable alloy nanocatalysts with controllable compositions.

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.

Enhancing Oxygen Reduction Activity of Pt-based Electrocatalysts: From Theoretical Mechanisms to Practical Methods.

Pt-based electrocatalysts are considered as one of the most promising choices to facilitate the oxygen reduction reaction (ORR), and the key factor enabling their success is to reduce the required amount of platinum. Herein, we focus on illuminating both the theoretical mechanisms which enable enhanced and sustained ORR activity and the practical methods to achieve them in catalysts. The various multi-step pathways of ORR are firstly reviewed and the rate-determining steps based on the reaction intermediates and their binding energies are analyzed. We then explain the critical aspects of Pt-based electrocatalysts to tune oxygen reduction properties from the viewpoints of active sites exposure and altering the surface electronic structure, and further summarize representative research progress towards practically achieving these activity enhancements with a focus on platinum size reduction, shape control and core Pt elimination methods. We finally outline the remaining challenges and provide our perspectives with regard to further enhancing their activities.

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.

In Situ Engineering of Intracellular Hemoglobin for Implantable High-Performance Biofuel Cells.

The key challenge for the broad application of implantable biofuel cells (BFCs) is to achieve inorganic-organic composite biocompatibility while improving the activity and selectivity of the catalysts. We have fabricated nanoengineered red blood cells (NERBCs) by an environmentally friendly method by using red blood cells as the raw material and hemoglobin (Hb) embedded with ultrasmall hydroxyapatite (HAP, Ca10 (PO4 )6 (OH)2 ) as the functional BFC cathode material. The NERBCs showed greatly enhanced cell performance with high electrocatalytic activity, stability, and selectivity. The NERBCs maintained the original biological properties of the natural cell, while enhancing the catalytic oxygen reduction reaction (ORR) through the interaction between -OH groups in HAP and the Hb in RBCs. They also enabled direct electron transportation, eliminating the need for an electron-transfer mediator, and showed catalytic inactivity for glucose oxidation, thus potentially enabling the development of separator-free BFCs.

Optical and Electrical Modulation Strategies of Photoelectrodes for Photoelectrochemical Water Splitting.

When constructing efficient, cost-effective, and stable photoelectrodes for photoelectrochemical (PEC) systems, the solar-driven photo-to-chemical conversion efficiency of semiconductors is limited by several factors, including the surface catalytic activity, light absorption range, carrier separation, and transfer efficiency. Accordingly, various modulation strategies, such as modifying the light propagation behavior and regulating the absorption range of incident light based on optics and constructing and regulating the built-in electric field of semiconductors based on carrier behaviors in semiconductors, are implemented to improve the PEC performance. Herein, the mechanism and research advancements of optical and electrical modulation strategies for photoelectrodes are reviewed. First, parameters and methods for characterizing the performance and mechanism of photoelectrodes are introduced to reveal the principle and significance of modulation strategies. Then, plasmon and photonic crystal structures and mechanisms are summarized from the perspective of controlling the propagation behavior of incident light. Subsequently, the design of an electrical polarization material, polar surface, and heterojunction structure is elaborated to construct an internal electric field, which serves as the driving force to facilitate the separation and transfer of photogenerated electron-hole pairs. Finally, the challenges and opportunities for developing optical and electrical modulation strategies for photoelectrodes are discussed.

Design and Algorithm Integration of High-Precision Adaptive Underwater Detection System Based on MEMS Vector Hydrophone.

Real-time DOA (direction of arrival) estimation of surface or underwater targets is of great significance to the research of marine environment and national security protection. When conducting real-time DOA estimation of underwater targets, it can be difficult to extract the prior characteristics of noise due to the complexity and variability of the marine environment. Therefore, the accuracy of target orientation in the absence of a known noise is significantly reduced, thereby presenting an additional challenge for the DOA estimation of the marine targets in real-time. Aiming at the problem of real-time DOA estimation of acoustic targets in complex environments, this paper applies the MEMS vector hydrophone with a small size and high sensitivity to sense the conditions of the ocean environment and change the structural parameters in the adaptive adjustments system itself to obtain the desired target signal, proposes a signal processing method when the prior characteristics of noise are unknown. Theoretical analysis and experimental verification show that the method can achieve accurate real-time DOA estimation of the target, achieve an error within 3.1° under the SNR (signal-to-noise ratio) of the X channel of -17 dB, and maintain a stable value when the SNR continues to decrease. The results show that this method has a very broad application prospect in the field of ocean monitoring.

Longevous Cycling of Rechargeable Zn-Air Battery Enabled by "Raisin-Bread" Cobalt Oxynitride/Porous Carbon Hybrid Electrocatalysts.

Developing commercially viable electrocatalyst lies at the research hotspot of rechargeable Zn-air batteries, but it is still challenging to meet the requirements of energy efficiency and durability in realistic applications. Strategic material design is critical to addressing its drawbacks in terms of sluggish kinetics of oxygen reactions and limited battery lifespan. Herein, a "raisin-bread" architecture is designed for a hybrid catalyst constituting cobalt nitride as the core nanoparticle with thin oxidized coverings, which is further deposited within porous carbon aerogel. Based on synchrotron-based characterizations, this hybrid provides oxygen vacancies and Co-Nx -C sites as the active sites, resulting from a strong coupling between CoOx Ny nanoparticles and 3D conductive carbon scaffolds. Compared to the oxide reference, it performs enhanced stability in harsh electrocatalytic environments, highlighting the benefits of the oxynitride. Furthermore, the 3D conductive scaffolds improve charge/mass transportation and boost durability of these active sites. Density functional theory calculations reveal that the introduced N species into hybrid can synergistically tune the d-band center of cobalt and improve its bifunctional activity. As a result, the obtained air cathode exhibits bifunctional overpotential of 0.65 V and a battery lifetime exceeding 1350 h, which sets a new record for rechargeable Zn-air battery reported so far.

Sulfide-Based All-Solid-State Lithium-Sulfur Batteries: Challenges and Perspectives.

Lithium-sulfur batteries with liquid electrolytes have been obstructed by severe shuttle effects and intrinsic safety concerns. Introducing inorganic solid-state electrolytes into lithium-sulfur systems is believed as an effective approach to eliminate these issues without sacrificing the high-energy density, which determines sulfide-based all-solid-state lithium-sulfur batteries. However, the lack of design principles for high-performance composite sulfur cathodes limits their further application. The sulfur cathode regulation should take several factors including the intrinsic insulation of sulfur, well-designed conductive networks, integrated sulfur-electrolyte interfaces, and porous structure for volume expansion, and the correlation between these factors into account. Here, we summarize the challenges of regulating composite sulfur cathodes with respect to ionic/electronic diffusions and put forward the corresponding solutions for obtaining stable positive electrodes. In the last section, we also outlook the future research pathways of architecture sulfur cathode to guide the develop high-performance all-solid-state lithium-sulfur batteries.

Reducing Carbonaceous Salts for Facile Fabrication of Monolayer Graphene.

Novel methods and mechanisms for graphene fabrication are of great importance in the development of materials science. Herein, a facile method to directly convert carbonaceous salts into high-quality freestanding graphene via a simple one-step redox reaction, is reported. The redox couple can be a combination of sodium borohydride (reductant) and sodium carbonate (oxidant), which can readily react with each other when evenly mixed/calcined and yield gram-scale, high-quality, contamination-free, micron-sized, freestanding graphene. More importantly, this method is applicable to a variety of input reductants and oxidants that are low cost and easily accessible. An in-depth investigation reveals that the carbonaceous oxidants can not only provide reduced carbon mass for graphene formation but also act as a self-template to guide the polymerization of carbon atoms following the pattern of the monolayer, six-carbon rings. In addition, the direct formation of graphene exhibits theoretically lower energy barriers than that of other allotropes such as fullerene and carbon nanotube. This facile, low-cost, scalable, and applicable method for mass production of high-quality graphene is expected to revolutionize graphene fabrication technology and boost its practical application to the industry level.

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.

Boosting oxygen reduction reaction kinetics through perturbating electronic structure of single-atom Fe-N3S1 catalyst with sub-nano FeS cluster.

Single atomic Fe-N4 catalyst exhibits a great prospect for oxygen reduction reaction (ORR) and adjusting the intrinsic coordination structure and the carbon matrix structure effectively improves the catalytic activity. However, controlling the active site coordination structure and its surrounding environment at atomic level remains a challenge. In this paper, Fe-N3S1 and FeS sub-nano cluster were innovatively concatenated on S, N co-doped carbon matrix (SNC), denoted as FeS/FeSA@SNC catalysts, for modulating ORR catalysis performance. Both experimental measurements and theoretical calculations have confirmed that the local electron configuration of Fe center is modulated by this unique structure combination leading to optimized ORR kinetics. Based on this design, the synthesized FeS/FeSA@SNC delivers ORR activity with a half-wave potential of 0.9 V (vs. RHE), excelling that of commercial Pt/C (0.87 V) and the Zn-air battery (ZAB) with this cathode catalyst delivers a peak power density of 126 mW cm-2. This work presents a novel strategy for manipulating the single-atom active sites through control the local coordination structure and provides a reference for the development of novel efficient ORR electrocatalysts.

Co-Fe3C pair sites catalyst with heterometallic dual active sites for efficient oxygen reduction reaction.

Newly emerging metal-based pair sites catalysts show great potential because they can provide more metal active centers with synergistic effect for green catalysis, compared with single site catalysts. However, both the synthesis and catalytic mechanisms of the pair sites catalyst with new structural features need to be developed vigorously to promote the desired chemical reactions, especially carbon-based metal catalysts for green energy storage and conversion devices. Herein, we constructed highly active Co-Fe3C pair sites on N-doped graphite catalyst (CNCo-Fe3C) by a two-step strategy, which have electron interactions of heterometallic atoms and can play better synergistic effect. X-ray absorption spectra and density functional theory (DFT) calculation further identify the presence of heterometallic active sites in the pair sites catalyst, resulting in electron redistribution and positive d-band center due to the electron interactions. The more positive d-band center model predicts the optimization of the adsorption energy of oxygen-containing intermediates, and reduces the energy barrier of the determining step. This further results in superior oxygen reduction reaction (ORR) performance with a half-wave potential of 0.90 V versus reversible hydrogen electrode (vs.RHE) and superior long-term stability for about 20 h with only 2.3 % decrease at 0.75 V vs.RHE in 0.1 M KOH solution. Additionally, it also shows significant peak power density of 124 mW cm-2 and prominent cycling stability performance exceeding 400 h at 5 mA cm-2 in the Zn-air battery (ZAB) test, which is higher than that of Pt/C catalyst. This work provides a new idea for the regulation of intrinsic activity of non-noble metal ORR catalysts through the synergistic effect of the pair sites.