Double-helical assembly of heterodimeric nanoclusters into supercrystals.

DNA has long been used as a template for the construction of helical assemblies of inorganic nanoparticles1-5. For example, gold nanoparticles decorated with DNA (or with peptides) can create helical assemblies6-9. But without such biological ligands, helices are difficult to achieve and their mechanism of formation is challenging to understand10,11. Atomically precise nanoclusters that are protected by ligands such as thiolate12,13 have demonstrated hierarchical structural complexity in their assembly at the interparticle and intraparticle levels, similar to biomolecules and their assemblies14. Furthermore, carrier dynamics can be controlled by engineering the structure of the nanoclusters15. But these nanoclusters usually have isotropic structures16,17 and often assemble into commonly found supercrystals18. Here we report the synthesis of homodimeric and heterodimeric gold nanoclusters and their self-assembly into superstructures. While the homodimeric nanoclusters form layer-by-layer superstructures, the heterodimeric nanoclusters self-assemble into double- and quadruple-helical superstructures. These complex arrangements are the result of two different motif pairs, one pair per monomer, where each motif bonds with its paired motif on a neighbouring heterodimer. This motif pairing is reminiscent of the paired interactions of nucleobases in DNA helices. Meanwhile, the surrounding ligands on the clusters show doubly or triply paired steric interactions. The helical assembly is driven by van der Waals interactions through particle rotation and conformational matching. Furthermore, the heterodimeric clusters have a carrier lifetime that is roughly 65 times longer than that of the homodimeric clusters. Our findings suggest new approaches for increasing complexity in the structural design and engineering of precision in supercrystals.

Differential Activation of Alkynes between Capped and Naked Ag Nanoclusters Anchored by Highly-Open Mesoporous CeO2 for Two Coupling Reactions with CO2.

The cyclization of 3-hydroxy alkynes and the carboxylation of terminal alkynes both with CO2 are two attractive strategies to simultaneously reduce CO2 emission and produce value-added chemicals. Herein, the differential activation of alkynes over atomically precise Ag nanoclusters (NCs) supported on Metal-organic framework-derived highly-open mesoporous CeO2 (HM-CeO2) by reserving or removing their surface captopril ligands is reported. The ligand-capped Ag NCs possess electron-rich Ag atoms as efficient π-activation catalytic sites in cyclization reactions, while the naked Ag NCs possess partial positive-charged Ag atoms as perfect σ-activation catalytic sites in carboxylation reactions. Impressively, via coupling with HM-CeO2 featuring abundant basic sites and quick mass transfer, the ligand-capped Ag NCs afford 97.9% yield of 4,4-dimethyl-5-methylidene-1,3-dioxolan-2-one for the cyclization of 2-methyl-3-butyn-2-ol with CO2, which is 4.5 times that of the naked Ag NCs (21.7%), while the naked Ag NCs achieve 98.5% yield of n-butyl 2-alkynoate for the carboxylation of phenylacetylene with CO2, which is 15.6 times that of ligand-capped Ag NCs (6.3%). Density functional theory calculations reveal the ligand-capped Ag NCs can effectively activate alkynyl carbonate ions for the intramolecular ring closing in cyclization reaction, while the naked Ag NCs are highly affiliative in stabilizing terminal alkynyl anions for the insertion of CO2 in carboxylation reaction.

Domestication of rice may have changed its arbuscular mycorrhizal properties by modifying phosphorus nutrition-related traits and decreasing symbiotic compatibility.

Modern cultivated rice (Oryza sativa) typically experiences limited growth benefits from arbuscular mycorrhizal (AM) symbiosis. This could be due to the long-term domestication of rice under favorable phosphorus conditions. However, there is limited understanding of whether and how the rice domestication has modified AM properties. This study compared AM properties between a collection of wild (Oryza rufipogon) and domesticated rice genotypes and investigated the mechanisms underlying their differences by analyzing physiological, genomic, transcriptomic, and metabolomic traits critical for AM symbiosis. The results revealed significantly lower mycorrhizal growth responses and colonization intensity in domesticated rice compared to wild rice, and this change of AM properties may be associated with the domestication modifications of plant phosphorus utilization efficiency at physiological and genomic levels. Domestication also resulted in a decrease in the activity of the mycorrhizal phosphorus acquisition pathway, which may be attributed to reduced mycorrhizal compatibility of rice roots by enhancing defense responses like root lignification and reducing carbon supply to AM fungi. In conclusion, rice domestication may have changed its AM properties by modifying P nutrition-related traits and reducing symbiotic compatibility. This study offers new insights for improving AM properties in future rice breeding programs to enhance sustainable agricultural production.

Superelastic oxide micropillars enabled by surface tension-modulated 90° domain switching with excellent fatigue resistance.

Superelastic materials capable of recovering large nonlinear strains are ideal for a variety of applications in morphing structures, reconfigurable systems, and robots. However, making oxide materials superelastic has been a long-standing challenge due to their intrinsic brittleness. Here, we fabricate ferroelectric BaTiO3 (BTO) micropillars that not only are superelastic but also possess excellent fatigue resistance, lasting over 1 million cycles without accumulating residual strains or noticeable variation in stress-strain curves. Phase field simulations reveal that the large recoverable strains of BTO micropillars arise from surface tension-modulated 90° domain switching and thus are size dependent, while the small energy barrier and ultralow energy dissipation are responsible for their unprecedented cyclic stability among superelastic materials. This work demonstrates a general strategy to realize superelastic and fatigue-resistant domain switching in ferroelectric oxides for many potential applications.

Passive leg raising modulates low-frequency oscillation propagation in peripheral atherosclerosis: A pilot study.

OBJECTIVE: Low-frequency oscillations (LFOs) observed in the periphery may reflect physiological processes. The aim of this study was to investigate these processes' effects on LFOs and the differences between healthy subjects and those with peripheral arteriosclerosis disease (PAD). METHODS: 14 PAD patients and 25 healthy controls were studied in resting (RS) and passive leg raising (PLR) states. We simultaneously measured LFOs at the peripheral left earlobes (LE), right earlobes (RE), left fingertips (LF), right fingertips (RF), left toes (LT), and right toes (RT), along with coherence and phase shift analysis processing. RESULTS: The coherence coefficients in the PAD group were lower than those in the healthy group (p < .01), and the phase shifts in the PAD group were higher than those in the healthy group (p < .01) in a resting state. Mild to moderate PAD patients had greater coherence coefficients and smaller phase shifts than severe PAD patients. 0.05 Hz PLR LFOs originating in the LT can be observed in other peripheral positions. The proportion of occurrence times for 0.05 Hz PLR LFOs peaks observed at different peripheral positions was different in healthy subjects, patients with bilateral multiple lower limb arteriosclerosis, and those with left or right lower limb arteriosclerosis. CONCLUSION: The coherence coefficient and phase shift characteristics of LFOs were different between healthy subjects and PAD patients. LFOs have the potential to provide valuable physiological process information associated with atherosclerosis in the periphery.

A Double Open-Shelled Au43 Nanocluster with Increased Catalytic Activity and Stability.

Atomically precise metal nanoclusters (NCs) are an intriguing class of crystalline solids with unique physicochemical properties derived from tunable structures and compositions. Most atomically precise NCs require closed-shells and coordinatively saturated surface metals in order to be stable. Herein, we report Au43(C≡CtBu)20 and Au42Ag1(C≡CtBu)20, which feature open electronic and geometric shells, leading to both paramagnetism (23 valence e-) and enhanced catalytic activity from a single coordinatively unsaturated surface metal. The Au-alkynyl surface motifs of these NCs form five helical stripes around the inner Au12 kernel, imparting chirality and high thermal stability. Density functional theory (DFT) calculations suggest that there are minimal energy differences between the open-shelled NCs and hypothetical closed-shell systems and that the open-shelled electronic configuration gives rise to the largest band gap, which is known to promote cluster stability. Furthermore, we highlight how coordinatively unsaturated surface metals create active sites for the catalytic oxidation of benzyl alcohol to benzaldehyde, leading to high selectivity and increased conversion. This work represents the first example of an atomically precise Au NC with a double open-shelled structure and provides a promising platform for investigating the magnetic and catalytic properties of noble metal nanoparticles.

Integrating Dual-Single-Atom Moieties with N, S Co-Coordination Configurations for Oxidative Cascaded Catalysis.

Oxidation reaction is of critical importance in chemical industry, in which the primary O2 activation step still calls for high-performance catalysts. Here, a newly developed precise locating carbonization strategy for the fabrication of 21 kinds of dual-metal single-atom catalysts with N, S co-coordinated configurations is reported. As is exemplified by CoN3 S1 /CuN4 @NC, systematical characterizations and in situ observations imply the atomic CoN3 S1 and CuN4 sites immobilized on N-doped carbon, over which the remarkable electron redistribution originating from their unsymmetrical coordination configurations. Impressively, the obtained CoN3 S1 /CuN4 @NC exhibits unprecedented capability in O2 activation and enables a spontaneous process through its dynamic configuration, significantly outperforming the CoN4 /CuN4 @NC and CoN3 S1 @NC counterparts. Hence, the CoN3 S1 /CuN4 @NC shows attractive performance in domino synthesis of natural flavone and 19 kinds of derivatives from benzyl alcohol, 2'-hydroxyacetophenone, and corresponding substituted substrates via aerobic oxidative coupling-dehydrogenation. Detailed reaction mechanisms and molecule behaviors over CoN3 S1 /CuN4 @NC are also investigated through in situ experiments and simulations.

Metal-Organic Frameworks as a New Platform to Construct Ordered Mesoporous Ce-Based Oxides for Efficient CO2 Fixation under Ambient Conditions.

Metal-organic frameworks (MOFs) are proved to be good precursors to derive various nanomaterials with desirable functions, but so far the controllable synthesis of ordered mesoporous derivatives from MOFs has not been achieved. Herein, this work reports, for the first time, the construction of MOF-derived ordered mesoporous (OM) derivatives by developing a facile mesopore-inherited pyrolysis-oxidation strategy. This work demonstrates a particularly elegant example of this strategy, which involves the mesopore-inherited pyrolysis of OM-CeMOF into a OM-CeO2 @C composite, followed by the oxidation removal of its residual carbon, affording the corresponding OM-CeO2 . Furthermore, the good tunability of MOFs helps to allodially introduce zirconium into OM-CeO2 to regulate its acid-base property, thus boosting its catalytic activity for CO2 fixation. Impressively, the optimized Zr-doped OM-CeO2 can achieve above 16 times higher catalytic activity than its solid CeO2 counterpart, representing the first metal oxide-based catalyst to realize the complete cycloaddition of epichlorohydrin with CO2 under ambient temperature and pressure. This study not only develops a new MOF-based platform for enriching the family of ordered mesoporous nanomaterials, but also demonstrates an ambient catalytic system for CO2 fixation.

Morphology-Engineering Construction of Anti-Aggregated Co/N-Doped Hollow Carbon from Metal-Organic Frameworks for Efficient Biomass Upgrading.

The controlled pyrolysis of metal/carbon-containing precursors is commonly used for fabricating multifunctional metal/carbon-based catalysts, nevertheless, the inevitable agglomeration of these precursors in pyrolysis is extremely negative for efficient catalysis. This study reports the first example of suppressing the interfacial fusion and agglomeration of metal/carbon-based catalyst in its pyrolysis-involved fabrication process by developing a facile morphology-engineering strategy. Metal-organic framework precursors are chosen as a proof of concept and five Co/N-doped hollow carbons with different morphologies (rhombic dodecahedron, cube, plate, interpenetration twin, and rod) are synthesized via the pyrolysis of their corresponding core-shell ZIF-8@ZIF-67 precursors. It is demonstrated that the interpenetration twin precursor shows the minimum interfacial contact of interparticles due to its partly-concave morphology with abundant facets, which endows it with the best resistibility from interfacial fusion and thus aggregation of interparticles during pyrolysis. Benefiting from its unique anti-aggregated structure with high specific surface area, abundant fully-exposed active sites, and good dispersibility, the resultant 36-facet Co/N-doped hollow carbon exhibit remarkably improved catalytic property for biomass upgrading as compared with its aggregated counterparts. This study highlights the crucial role of engineering morphology to prevent metal/carbon-containing precursors from detrimental agglomeration during pyrolysis, demonstrating a new approach to constructing anti-aggregated metal/carbon-based catalysts.

Coupling Hydrazine Oxidation with Seawater Electrolysis for Energy-Saving Hydrogen Production over Bifunctional CoNC Nanoarray Electrocatalysts.

Seawater electrolysis is a promising method to produce H2 without relying on scarce freshwater resource, but its high energy consumption and inevitable accompany of competitive chlorine oxidation reaction (ClOR) are still great technological challenges. Herein, a metal-organic framework (MOF)-templated pyrolysis strategy to prepare uniform cobalt/nitrogen-codoped carbon nanosheet arrays on carbon cloth (CC@CoNC) as highly-efficient but low-cost bifunctional electrocatalysts for hydrazine-assisted seawater electrolysis is explored. The optimized CoNC nanosheet arrays can be used as an efficient bifunctional electrocatalyst to catalyze hydrazine oxidation reaction and hydrogen evolution reaction, remarkably reducing the energy consumption and nicely overcome the undesired anodic corrosion problems caused by ClOR. Impressively, a hydrazine-assisted water electrolysis system is successfully assembled by using the optimized CC@CoNC as both cathode and anode, which only needs an ultra-low cell voltage of 0.557 V and an electricity consumption of 1.22 kW h per cubic meter of H2 to achieve 200 mA cm-2 . Furthermore, the optimized CC@CoNC can also show greatly improved stability in the hydrazine-assisted seawater electrolysis system for H2 production, which can work steadily for above 40 h at ≈10 mA cm-2 . This study may offer great opportunities for obtaining hydrogen energy from infinite ocean resource by an eco-friendly method.

Toward Active-Site Tailoring in Heterogeneous Catalysis by Atomically Precise Metal Nanoclusters with Crystallographic Structures.

Heterogeneous catalysis involves solid-state catalysts, among which metal nanoparticles occupy an important position. Unfortunately, no two nanoparticles from conventional synthesis are the same at the atomic level, though such regular nanoparticles can be highly uniform at the nanometer level (e.g., size distribution ∼5%). In the long pursuit of well-defined nanocatalysts, a recent success is the synthesis of atomically precise metal nanoclusters protected by ligands in the size range from tens to hundreds of metal atoms (equivalently 1-3 nm in core diameter). More importantly, such nanoclusters have been crystallographically characterized, just like the protein structures in enzyme catalysis. Such atomically precise metal nanoclusters merge the features of well-defined homogeneous catalysts (e.g., ligand-protected metal centers) and enzymes (e.g., protein-encapsulated metal clusters of a few atoms bridged by ligands). The well-defined nanoclusters with their total structures available constitute a new class of model catalysts and hold great promise in fundamental catalysis research, including the atomically precise size dependent activity, control of catalytic selectivity by metal structure and surface ligands, structure-property relationships at the atomic-level, insights into molecular activation and catalytic mechanisms, and the identification of active sites on nanocatalysts. This Review summarizes the progress in the utilization of atomically precise metal nanoclusters for catalysis. These nanocluster-based model catalysts have enabled heterogeneous catalysis research at the single-atom and single-electron levels. Future efforts are expected to achieve more exciting progress in fundamental understanding of the catalytic mechanisms, the tailoring of active sites at the atomic level, and the design of new catalysts with high selectivity and activity under mild conditions.

A Bibliometric Analysis for Low-Intensity Ultrasound Study Over the Past Three Decades.

Low-intensity ultrasound (LI-US) is a non-invasive stimulation technique that has emerged in recent years and has been shown to have positive effects on neuromodulation, fracture healing, inflammation improvement, and metabolic regulation. This study reports the conclusions of a bibliometric analysis of LI-US. Input data for the period between 1995 and 2022, including 7209 related articles in the field of LI-US, were collected from the core library of the Web of Science (WOS) database. Using these data, a set of bibliometric indicators was obtained to gain knowledge on different aspects: global production, research areas, and sources analysis, contributions of countries and institutions, author analysis, citation analysis, and keyword analysis. This study combined the data analysis capabilities provided by the WOS database, making use of two bibliometric software tools: R software and VOS viewer to achieve analysis and data exploration visualization, and predicted the further development trends of LI-US. It turns out that the United States and China are co-leaders while Zhang ZG is the most significant author in LI-US. In the future, the hot spots of LI-US will continue to focus on parameter research, mechanism discussion, safety regulations, and neuromodulation applications.

Seasonal dissemination of antibiotic resistome from livestock farms to surrounding soil and air: Bacterial hosts and risks for human exposure.

Feces in livestock farms is a reservoir of antibiotic resistance genes (ARGs), which can disseminate into surrounding soil and air, bringing risks to human health. In this study, seasonal dissemination of ARGs in a livestock farm and implications for human exposure was explored. The experimental results showed that ARGs abundance basically ranked as feces > soil > air, and significant seasonal dependence was observed. The total ARGs in pig feces was relatively higher in autumn (109.7 copies g-1) and winter (1010.0 copies g-1), and lower in summer (105.0 copies g-1). Similarly, the lowest total ARGs in soil and air were also observed in summer. There were correlations among ARGs, integron intI1, and bacterial community. Total organic carbon was an important factor affecting ARGs distribution in the feces, and pH and moisture content significantly affected soil ARGs. The daily intakes of integron intI1 and ARGs from air were 10°.5 copies h-1 and 102.3 copies h-1 for human exposure, respectively. Pseudomonas was a potential pathogenic host of blaTEM-1 in feces, Pseudomonas and Acinetobacter were potential pathogenic hosts of multiple ARGs in soil, while ARGs in air did not migrate into pathogens.

Photo-Induced Switching of CO2 Hydrogenation Pathway towards CH3 OH Production over Pt@UiO-66-NH2 (Co).

It is highly desired to achieve controllable product selectivity in CO2 hydrogenation. Herein, we report light-induced switching of reaction pathways of CO2 hydrogenation towards CH3 OH production over actomically dispersed Co decorated Pt@UiO-66-NH2 . CO, being the main product in the reverse water gas shift (RWGS) pathway under thermocatalysis condition, is switched to CH3 OH via the formate pathway with the assistance of light irradiation. Impressively, the space-time yield of CH3 OH in photo-assisted thermocatalysis (1916.3 µmol gcat -1 h-1 ) is about 7.8 times higher than that without light at 240 °C and 1.5 MPa. Mechanism investigation indicates that upon light irradiation, excited UiO-66-NH2 can transfer electrons to Pt nanoparticles and Co sites, which can efficiently catalyze the critical elementary steps (i.e., CO2 -to-*HCOO conversion), thus suppressing the RWGS pathway to achieve a high CH3 OH selectivity.

Defect Engineered Metal-Organic Framework with Accelerated Structural Transformation for Efficient Oxygen Evolution Reaction.

Metal-organic frameworks (MOFs) have been increasingly applied in oxygen evolution reaction (OER), and the surface of MOFs usually undergoes structural transformation to form metal oxyhydroxides to serve as catalytically active sites. However, the controllable regulation of the reconstruction process of MOFs remains as a great challenge. Here we report a defect engineering strategy to facilitate the structural transformation of MOFs to metal oxyhydroxides during OER with enhanced activity. Defective MOFs (denoted as NiFc'x Fc1-x ) with abundant unsaturated metal sites are constructed by mixing ligands of 1,1'-ferrocene dicarboxylic acid (Fc') and defective ferrocene carboxylic acid (Fc). NiFc'x Fc1-x series are more prone to be transformed to metal oxyhydroxides compared with the non-defective MOFs (NiFc'). Moreover, the as-formed metal oxyhydroxides derived from defective MOFs contain more oxygen vacancies. NiFc'Fc grown on nickel foam exhibits excellent OER catalytic activity with an overpotential of 213 mV at the current density of 100 mA cm-2 , superior to that of undefective NiFc'. Experimental results and theoretical calculations suggest that the abundant oxygen vacancies in the derived metal oxyhydroxides facilitate the adsorption of oxygen-containing intermediates on active centers, thus significantly improving the OER activity.

Template-Oriented Polyaniline-Supported Palladium Nanoclusters for Reductive Homocoupling of Furfural Derivatives.

Developing well-defined structures and desired properties for porous organic polymer (POP) supported catalysts by controlling their composition, size, and morphology is of great significance. Herein, we report a preparation of polyaniline (PANI) supported Pd nanoparticles (NPs) with controllable structure and morphology. The protocol involves the introduction of MnO2 with different crystal structures (α, ß, γ, δ, ϵ) serving as both the reaction template and the oxidant. The different forms of MnO2 each convert aniline to a PANI that contains a unique regular distribution of benzene and quinone. This leads to the Pd/PANI catalysts with different charge transfer properties between Pd and PANI, as well as different dispersions of the metal NPs. In this case, the Pd/ϵ-PANI catalyst greatly improves the turnover frequency (TOF; to 88.3 h-1 ), in the reductive coupling of furfural derivatives to potential bio-based plasticizers. Systematic characterizations reveal the unique oxidation state of the support in the Pd/ϵ-PANI catalyst and coordination mode of Pd that drives the formation of highly dispersed Pd nanoclusters. Density functional theory (DFT) calculations show the more electron rich Pd/PANI catalyst has the lower energy barrier in the oxidative addition step, which favors the C-C coupling reaction.

Modulating the Reaction Configuration by Breaking the Structural Symmetry of Active Sites for Efficient Photocatalytic Reduction of Low-concentration CO2.

Photocatalytic conversion of low-concentration CO2 is considered as a promising way to simultaneously mitigate the environmental and energy issues. However, the weak CO2 adsorption and tough CO2 activation process seriously compromise the CO production, due to the chemical inertness of CO2 molecule and the formed fragile metal-C/O bond. Herein, we designed and fabricated oxygen vacancy contained Co3 O4 hollow nanoparticles on ordered macroporous N-doped carbon framework (Vo-HCo3 O4 /OMNC) towards photoreduction of low-concentration CO2 . In situ spectra and ab initio molecular dynamics simulations reveal that the constructed oxygen vacancy is able to break the local structural symmetry of Co-O-Co sites. The formation of asymmetric active site switches the CO2 configuration from a single-site linear model to a multiple-sites bending one with a highly stable configuration, enhancing the binding and structural polarization of CO2 molecules. As a result, Vo-HCo3 O4 /OMNC shows unprecedent activity in the photocatalytic conversion of low-concentration CO2 (10 % CO2 /Ar) under laboratory light source or even natural sunlight, affording a syngas yield of 337.8 or 95.2 mmol g-1 h-1 , respectively, with an apparent quantum yield up to 4.2 %.

Atomically Precise Au42 Nanorods with Longitudinal Excitons for an Intense Photothermal Effect.

Metallic-state gold nanorods are well known to exhibit strong longitudinal plasmon excitations in the near-infrared region (NIR) suitable for photothermal conversion. However, when the size decreases below ∼2 nm, Au nanostructures become nonmetallic, and whether the longitudinal excitation in plasmonic nanorods can be inherited is unknown. Here, we report atomically precise rod-shaped Au42(SCH2Ph)32 with a hexagonal-close-packed Au20 kernel of aspect ratio as high as 6.2, which exhibits an intense absorption at 815 nm with a high molar absorption coefficient of 1.4 × 105 M-1 cm-1. Compared to other rod-shaped nanoclusters, Au42 possesses a much more effective photothermal conversion with a large temperature increase of ∼27 °C within 5 min (λex = 808 nm, 1 W cm-2) at an ultralow concentration of 50 µg mL-1 in toluene. Density functional theory calculations show that the NIR transition is mainly along the long axis of the Au20 kernel in Au42, i.e., a longitudinal excitonic oscillation, akin to the longitudinal plasmon in metallic-state nanorods. Transient absorption spectroscopy reveals that the fast decay in Au42 is similar to that of shorter-aspect-ratio nanorods but is followed by an additional slow decay with a long lifetime of 2400 ns for the Au42 nanorod. This work provides the first case that an intense longitudinal excitation is obtained in molecular-like nanorods, which can be used as photothermal converters and hold potential in biomedical therapy, photoacoustic imaging, and photocatalysis.

Controllable Synthesis of Ultrathin Defect-Rich LDH Nanoarrays Coupled with MOF-Derived Co-NC Microarrays for Efficient Overall Water Splitting.

Water electrolysis has attracted immense research interest, nevertheless the lack of low-cost but efficient bifunctional electrocatalysts for both hydrogen and oxygen evolution reactions greatly hinders its commercial applications. Herein, the controllable synthesis of ultrathin defect-rich layered double hydroxide (LDH) nanoarrays assembled on metal-organic framework (MOF)-derived Co-NC microarrays for boosting overall water splitting is reported. The Co-NC microarrays can not only provide abundant nucleation sites to produce a large number of LDH nuclei for favoring the growth of ultrathin LDHs, but also help to inhibit their tendency to aggregate. Impressively, five types of ultrathin bimetallic LDH nanoarrays can be electrodeposited on the Co-NC microarrays, forming desirable nanoarray-on-macroarray architectures, which show high uniformity with thicknesses from 1.5 to 1.9 nm. As expected, the electrocatalytic performance is significantly enhanced by exploiting the respective advantages of Co-NC microarrays and ultrathin LDH nanoarrays as well as the potential synergies between them. Especially, the optimal Co-NC@Ni2 Fe-LDH as both cathode and anode can afford the lowest cell voltage of 1.55 V at 10 mA cm-2 , making it one of the best earth-abundant bifunctional electrocatalysts for water electrolysis. This study provides new insights into the rational design of highly-active and low-cost electrocatalysts and facilitates their promising applications in the fields of energy storage and conversion.

Main-Group Metal Single-Atomic Regulators in Dual-Metal Catalysts for Enhanced Electrochemical CO2 Reduction.

Single-atom sites can not only act as active centers, but also serve as promising catalyst regulators and/or promoters. However, in many complex reaction systems such as electrochemical CO2 reduction reaction (CO2 RR), the introduction of single-atom regulators may inevitably induce the competitive hydrogen evolution reaction (HER) and thus reduce the selectivity. Here, the authors demonstrate that introducing HER-inert main-group metal single atoms adjacent to transition-metal single atoms can modify their electronic structure to enhance the CO2 RR to CO without inducing the HER side reaction. Dual-metal Cu and In single-site atoms anchored on mesoporous nitrogen-doped carbon (denoted as Cu-In-NC) are prepared by the pyrolysis of a multimetallic metal-organic framework. Cu-In-NC shows a high faradic efficiency of 96% toward CO formation at -0.7 V versus reversible hydrogen electrode, superior to that of its monometallic single-atom counterparts. Density functional theory studies reveal that the HER-inert In sites can activate the adjacent Cu sites through electronic modifications, strengthening the binding of *COOH intermediate and thus boosting the electrochemical reduction of CO2 to CO.