Review on strategies for improving the added value and expanding the scope of CO2 electroreduction products.

The electrochemical reduction of CO2 into value-added chemicals has been explored as a promising solution to realize carbon neutrality and inhibit global warming. This involves utilizing the electrochemical CO2 reduction reaction (CO2RR) to produce a variety of single-carbon (C1) and multi-carbon (C2+) products. Additionally, the electrolyte solution in the CO2RR system can be enriched with nitrogen sources (such as NO3-, NO2-, N2, or NO) to enable the synthesis of organonitrogen compounds via C-N coupling reactions. However, the electrochemical conversion of CO2 into valuable chemicals still faces challenges in terms of low product yield, poor faradaic efficiency (FE), and unclear understanding of the reaction mechanism. This review summarizes the promising strategies aimed at achieving selective production of diverse carbon-containing products, including CO, formate, hydrocarbons, alcohols, and organonitrogen compounds. These approaches involve the rational design of electrocatalysts and the construction of coupled electrocatalytic reaction systems. Moreover, this review presents the underlying reaction mechanisms, identifies the existing challenges, and highlights the prospects of the electrosynthesis processes. The aim is to offer valuable insights and guidance for future research on the electrocatalytic conversion of CO2 into carbon-containing products of enhanced value-added potential.

An Anchored Fe-Cu LDH onto a Polyvinylidene Fluoride Membrane with Strong Peroxymonosulfate Activation-Induced Degradation of Methylene Blue and Self-Cleaning Property of Oil/Water Separation.

Developing a strong catalytic antifouling membrane to achieve efficient sewage purification has great potential for alleviating water crisis. In this work, we designed and prepared an Fe/Cu-layered double hydroxide (Fe-Cu LDH)-coated polyvinylidene fluoride (PVDF) composite membrane (PVDF/Fe-Cu LDHs) with strong antifouling and activating peroxymonosulfate (PMS) catalytic degradation performance through polydopamine-coordination anchoring and hydrothermal reaction. The results showed that abundant hydroxyl groups of the LDH surface endowed the superhydrophilicity (water contact angle <10°) and underwater superoleophobicity (underwater-oil contact angle >150°) of the membrane surface, which displayed outstanding resistance to crude oil adhesion. With assistance of the LDH surface-bound sulfate radical of the peroxymonosulfate system, the PVDF/Fe-Cu LDH membrane demonstrated robust catalytic degradation performance for the methylene blue (MB) in the dark; the degradation rate constant (k, min-1) reached 0.96. Meanwhile, facing the oily wastewater, the selective wettability and charge effect of LDH of the surface made the PVDF/Fe-Cu LDH membrane realize the separation for the various surfactant-free and surfactant-stabilized emulsions. Importantly, the PMS-activation catalytic produced the ROS (•SO4-,•OH, •O2-, and 1O2), which enhanced the regeneration of the fouled PVDF/Fe-Cu LDH membrane and obtained a high flux recovery ratio in the dark (94.7%) after 10 cycles of separation experiments. Hence, we believed that the PVDF/Fe-Cu LDH membrane can provide inspiration for the development and further practical application of antifouling membranes.

One-Step Prepared Multifunctional Polyacrylonitrile/MIL-100(Fe) Membrane with High-Density Porous Fibers for Efficient Dye/Oil Wastewater Remediation.

With environmental pollution becoming more serious, developing efficient treatment technologies for all kinds of organic wastewater has become the focus of current research. In this work, the coaxial electrospinning technology was used to one-step fabricate a porous and underwater superoleophobic polyacrylonitrile nanofibrous membrane with an Fe-based metal-organic framework (MIL-100(Fe)). Benefiting from the synergistic effect of two jets, the nanofibers are smaller and denser, which prompt the exposure of more nanomaterial additives (MIL-100(Fe)). The BET surface area increased to 202.888 m2/g, and the membranes demonstrated outstanding underwater superoleophobicity. Moreover, compared with traditional blended matrix membranes by the single-axis method, separation of the modifier and membrane matrix material by coaxial methods also maintained excellent mechanical properties, which enhanced Young's modulus 3.4 times (∼1.34 MPa). As a result, facing soluble dyes, the porous C-PAN/MIL-100(Fe) membrane can demonstrate outstanding and fast adsorptive property (the Qm of MB and CR reached 44.71 and 88.74 mg g-1, respectively). For oily emulsion, the hydrophilic and oleophobic nanofibrous reticular surface provided excellent separation performance (flux: 1124.0-1549.3 L m-2 h-1, R > 98%). Moreover, the porous and underwater superoleophobic C-PAN/MIL-100(Fe)-0.5 membrane can synchronously purify the dye/oil mixture emulsions by one-step filtration. Based on the above performance, we believe that the modified nanofibrous membrane prepared by one-step coaxial electrospinning technology can promote more studies of the development of membrane preparation technology in the field of oily wastewater treatment.

Ultrafast Thermal Shock Synthesis and Porosity Engineering of 3D Hierarchical Cu-Bi Nanofoam Electrodes for Highly Selective Electrochemical CO2 Reduction.

Massive production of practical metal or alloy based electrocatalysts for electrocatalytic CO2 reduction reaction is usually limited by energy-extensive consumption, poor reproducibility, and weak adhesion on electrode substrates. Herein, we report the ultrafast thermal shock synthesis and porosity engineering of free-standing Cu-Bi bimetallic nanofoam electrocatalysts with 3D hierarchical porous structure and easily adjustable compositions. During the thermal shock process, the rapid heating and cooling steps in several seconds result in strong interaction between metal nanopowders to form multiphase nanocrystallines with abundant grain boundaries and metastable CuBi intermetallic phase. The subsequent porosity engineering process via acid etching and electroreduction creates highly porous Cu-Bi structures that can increase electrochemically active surface area and facilitate mass/charge transfer. Among the Cu-Bi nanofoam electrodes with different Cu/Bi ratios, the Cu4Bi nanofoam exhibited the highest formate selectivity with a Faradaic efficiency of 92.4% at -0.9 V (vs reversible hydrogen electrode) and demonstrated excellent operation stability.

Rapid and Green Electric-Explosion Preparation of Spherical Indium Nanocrystals with Abundant Metal Defects for Highly-Selective CO2 Electroreduction.

Electrochemical conversion of CO2 into high-value-added chemicals has been considered a promising route to achieve carbon neutrality and mitigate the global greenhouse effect. However, the lack of highly efficient electrocatalysts has limited its practical application. Herein, we propose an ultrafast and green electric explosion method to batch-scale prepare spherical indium (In) nanocrystals (NCs) with abundant metal defects toward high selective electrocatalytic CO2 reduction (CO2RR) to HCOOH. During the electric explosion synthesis process, the Ar atmosphere plays a significant role in forming the spherical In NCs with abundant metal defects instead of highly crystalline In2O3 NCs formed under an air atmosphere. Analysis results reveal that the In NCs possess ultrafast catalytic kinetics and reduced onset potential, which is ascribed to the formation of rich metal defects serving as effective catalytic sites for converting CO2 into HCOOH. This work provides a feasible strategy to massively produce efficient In-based electrocatalysts for electrocatalytic CO2-to-formate conversion.

High-sensitivity long-range surface plasmon resonance sensing assisted by gold nanoring cavity arrays and nanocavity coupling.

In many of the existing refractive index (RI) sensing works, only the shape and size of plasmonic structures are usually taken into account, while the parameters of spacer layers are ignored. In this publication, we explored the long-range surface plasmon resonance (LRSPR) and Fabry-Pérot resonance coupling effects of our proposed gold nanoring cavity array/spacer layer/Au mirror/glass substrate. Both the RI sensitivity and full width at half-maximum (FWHM) values were superior than those of conventional surface plasmon resonance substrates. We discussed the tunability of the RI sensitivity through changing the RI and thickness of the spacer layer. Then, under the optimized parameter conditions of the spacer layer, the geometry parameters (including size, gap and periodicity) of gold nanoring cavity arrays were tuned to optimize the best RI sensitivity. Finally, we broke the structural symmetry of a nanoring cavity to introduce Fano resonances into our system, and a high RI sensitivity and figure-of-merit (FOM) of 695 nm per RIU (refractive index unit) and 96.5, respectively, were achieved when the breaking angle θ was 30°. This study opens up many possibilities for boosting the FOM of RI sensing by taking into account the hybridization effects of localized surface plasmon resonance, LRSPR, and Fabry-Pérot and Fano resonances.

Yttrium- and Cerium-Codoped Ultrathin Metal-Organic Framework Nanosheet Arrays for High-Efficiency Electrocatalytic Overall Water Splitting.

The construction of low-cost, highly efficient, and stable electrocatalysts is a significant challenge for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, we report a facile strategy to fabricate ultrathin metal-organic framework (MOF) nanosheet arrays doped with two rare-earth elements, Y and Ce, and self-supported on nickel foam (NF) to enhance the HER and OER performance by constructing abundant active sites and bimetallic synergistic effects. The NiYCe-MOF/NF features an ultrathin nanosheet array structure and is uniformly and richly codoped by Y and Ce. When it was explored as both the anode and cathode electrocatalysts for overall water splitting, it achieved 10 mA cm-2 at 136 and 245 mV for the HER and OER in an alkaline electrolyte, respectively. Notably, an extremely low cell voltage of 1.54 V was required to achieve 100 mA cm-2 in 1.0 M KOH solution, making it a promising substitute for noble-metal catalysts.

Quasi-Phthalocyanine Conjugated Covalent Organic Frameworks with Nitrogen-Coordinated Transition Metal Centers for High-Efficiency Electrocatalytic Ammonia Synthesis.

Developing high-performance nitrogen reduction reaction (NRR) electrocatalysts is an ongoing challenge. Herein, we report a pyrolysis-free synthetic method for introducing ordered quasi-phthalocyanine N-coordinated transition metal (Ti, Cu, or Co) centers into a conjugated two-dimensional (2D) covalent organic framework (COF) for enhanced NRR performance. Detailed experiments and characterizations revealed that the NRR activity of Ti-COF was clearly better than that of Cu-COF and Co-COF, because of the superior abilities of Ti metal centers in activating inert N2 molecules and suppressing the hydrogen evolution reaction (HER). The resulting Ti-COF exhibits a high NH3 yield of 26.89 µg h-1 mg-1cat. and a Faradaic efficiency of 34.62% for NRR. Density functional theory (DFT) calculations verify that Ti-COF can effectively adsorb and activate N2 molecules and inhibit HER compared with Cu-COF, Co-COF, and pristine COF catalysts. This work opens a new avenue for developing 2D-COF materials that contain abundant coordinated transition metal centers toward electrocatalytic NRR.

Interfacial Reduction Nucleation of Noble Metal Nanodots on Redox-Active Metal-Organic Frameworks for High-Efficiency Electrocatalytic Conversion of Nitrate to Ammonia.

Electrochemically converting nitrate to ammonia is a promising route to realize artificial nitrogen recycling. However, developing highly efficient electrocatalysts is an ongoing challenge. Herein, we report the construction of stable and redox-active zirconium metal-organic frameworks (Zr-MOFs) based on Zr6 nanoclusters and redox-reversible tetrathiafulvalene (TTF) derivatives as inorganic nodes and organic linkers, respectively. The redox-active Zr-MOF can facilitate the in situ reduction of noble metal precursors free of external reductants and realize the uniform nucleation of noble metal nanodots (NDs) on Zr-MOF, achieving the preparation of M-NDs/Zr-MOF (M = Pd, Ag, or Au). The highly porous Zr-MOF with good conductivity can facilitate the mass transfer process. Among the M-NDs/Zr-MOF catalysts, Pd-NDs/Zr-MOF exhibits the highest electrocatalytic activity, delivering a NH3 yield of 287.31 mmol·h-1·g-1cat. and a Faradaic efficiency of 58.1%. The proposed interfacial reduction nucleation strategy for anchoring M NDs on Zr-MOFs can be applied to other challenging energy conversion reactions.

2D Arsenene and Arsenic Materials: Fundamental Properties, Preparation, and Applications.

As emerging 2D materials, arsenene and arsenic materials have attracted rising interest in the past few years. The diverse crystalline phases, exotic electrical characteristics, and widespread applications of 2D arsenene and arsenic bring them great research value and utilization potential. Herein, the recent progress of 2D arsenene and arsenic is reviewed in terms of fundamental properties, preparation, and applications. The fundamental properties of 2D arsenene and arsenic, including the crystal phases, environmental stability, and electrical structure, from theoretical to experimental reports are first summarized. Then, the experimental processes for preparing 2D arsenene and arsenic, along with their respective advantages and disadvantages, are introduced including epitaxial growth, mechanical exfoliation, and liquid-phase exfoliation. Moreover, applications of 2D arsenene and arsenic are discussed, suggesting a wide range of applications of 2D arsenene and arsenic in field-effect transistors, sensors, catalysts, biological applications, and so on. Finally, some perspectives about the challenges and opportunities of promising 2D arsenene and arsenic are provided. This review provides a helpful guidance and stimulates more focus on future explorations and developments of 2D arsenene and arsenic.

Batch-Scale Synthesis of Nanoparticle-Agminated Three-Dimensional Porous Cu@Cu2O Microspheres for Highly Selective Electrocatalysis of Nitrate to Ammonia.

The electrochemical nitrate reduction reaction (NITRR), which converts nitrate to ammonia, is promising for artificial ammonia synthesis at mild conditions. However, the lack of favorable electrocatalysts has hampered its large-scale applications. Herein, we report the batch-scale synthesis of three-dimensional (3D) porous Cu@Cu2O microspheres (Cu@Cu2O MSs) composed of fine Cu@Cu2O nanoparticles (NPs) using a convenient electric explosion method with outstanding activity and stability for the electrochemical reduction of nitrate to ammonia. Density functional theory (DFT) calculations revealed that the Cu2O (111) facets could facilitate the formation of *NO3H and *NO2H intermediates and suppress the hydrogen evolution reaction (HER), resulting in high selectivity for the NITRR. Moreover, the 3D porous structure of Cu@Cu2O MSs facilitates electrolyte penetration and increases the localized concentration of reactive species for the NITRR. As expected, the obtained Cu@Cu2O MSs exhibited an ultrahigh NH3 production rate of 327.6 mmol·h-1·g-1cat. (which is superior to that of the Haber-Bosch process with a typical NH3 yield <200 mmol h-1g-1cat.), a maximum Faradaic efficiency of 80.57%, and remarkable stability for the NITRR under ambient conditions. Quantitative 15N isotope labeling experiments indicated that the synthesized ammonia originated from the electrochemical reduction of nitrate. Achieving the batch-scale and low-cost production of high-performance Cu@Cu2O MSs electrocatalysts using the electric explosion method is promising for the large-scale realization of selective electrochemical reduction of nitrate toward artificial ammonia synthesis.

Nanocapillarity and Nanoconfinement Effects of Pipet-like Bismuth@Carbon Nanotubes for Highly Efficient Electrocatalytic CO2 Reduction.

Electrocatalytic CO2 reduction reaction is regarded as an intriguing route for producing renewable chemicals and fuels, but its development is limited by the lack of highly efficient and stable electrocatalysts. Herein, we propose the pipet-like bismuth (Bi) nanorods semifilled in nitrogen-doped carbon nanotubes (Bi-NRs@NCNTs) for highly selective electrocatalytic CO2 reduction. Benefited from the prominent capillary and confinement effects, the Bi-NRs@NCNTs act as nanoscale conveyors that can significantly facilitate the mass transport, adsorption,and concentration of reactants onto the active sites, realizing rapid reaction kinetics and low cathodic polarization. The spatial encapsulation and separation by the NCNT shells prevents the self-aggregation and surface oxidation of Bi-NRs, increasing the dispersity and stability of the electrocatalyst. As a result, the Bi-NRs@NCNTs exhibit high activity and durable catalytic stability for CO2-to-formate conversion over a wide potential range. The Faradaic efficiency for formate production reaches 90.9% at a moderate applied potential of -0.9 V vs reversible hydrogen electrode (RHE).

Rh/Al Nanoantenna Photothermal Catalyst for Wide-Spectrum Solar-Driven CO2 Methanation with Nearly 100% Selectivity.

Solar-powered CO2 conversion represents a promising green and sustainable approach for achieving a carbon-neutral economy. However, the rational design of a wide-spectrum sunlight-driven catalysis system for effective CO2 reduction is an ongoing challenge. Herein, we report the preparation of a rhodium/aluminum (Rh/Al) nanoantenna photothermal catalyst that can utilize a broad range of sunlight (from ultraviolet to the near-infrared region) for highly efficient CO2 methanation, achieving a high CH4 selectivity of nearly 100% and an unprecedented CH4 productivity of 550 mmol·g-1·h-1 under concentrated simulated solar irradiation (11.3 W·cm-2). Detailed control experiment results verified that the CO2 methanation process was facilitated by the localized surface plasmonic resonance and nanoantenna effects of the Rh/Al nanostructure under light irradiation. In operando temperature-programmed Fourier transform infrared spectroscopy confirmed that CO2 methanation on the Rh/Al nanoantenna catalyst was a multistep reaction with CO as a key intermediate. The design of a wide-spectrum solar-driven photothermal catalyst provides a feasible strategy for boosting CO2-to-fuel conversion.

High-performance colorimetric sensor based on PtRu bimetallic nanozyme for xanthine analysis.

The identification and quantification of xanthine are crucial for assessing the freshness and quality of food products, particularly in the seafood industry. Herein, a new approach was developed, involving the in-situ controllable growth of Pt91Ru9 nanoparticles on graphitic carbon nitride to yield Pt91Ru9@C3N4 catalytic materials. By integrating Pt91Ru9@C3N4 with the xanthine/xanthine oxidase (XOD) enzyme catalytic system, a nanozyme-enzyme tandem platform was obtained for the quantification analysis of xanthine. Under the catalytic oxidation of xanthine by XOD in the presence O2, H2O2 was generated. Upon the addition of peroxidase-like activity of Pt91Ru9@C3N4, H2O2 can be decomposed into •OH and 1O2, which can further catalyze the oxidation of TMB to its oxidation product oxTMB with an absorption peak at 652 nm. This smartphone-assisted portable colorimetric sensor for visual monitoring xanthine with a low detection limit of 8.92 nmol L-1, and successfully applied to detect xanthine in grass carp and serum samples.

Ratio-fluorescence sensor based on carbon dots and PtRu/CN nanozyme for efficient detection of melatonin in tablet.

The identification and quantification of melatonin (MT) are crucial for early diagnosis of disorders associated with circadian rhythm disruption. Herein, novel blue-emissive carbon dots (BCDs) were synthesized through an improved hydrothermal treatment using serine and malic acid as reductant and carbon source. The excellent optical properties of the as-obtained BCDs were used for ratiometric sensing by strategically constructing a MT sensing system integrating BCDs with C3N4 nanosheets loaded with platinum/ruthenium nanoparticles (PtRu/CN). In this system, H2O2 activated the peroxidase-like activity of PtRu/CN to generate •OH and 1O2 for oxidizing the colorless o-phenylenediamine (OPD) into yellow 2,3-diaminophenazine (DAP) with fluorescence emission at 565 nm. Concurrently, the fluorescence emission of BCDs at 439 nm was quenched by the generated DAP via the static quenching and inner filter effect (IFE) process. However, MT rapidly scavenged the generated free radicals to reverse the ratio fluorescence signal. The developed BCDs/PtRu/CN/OPD/H2O2 sensing platform enabled quantitative analysis of MT at concentrations ranging from 0.06 to 600 µmol/L with a low detection limit of 23.56 nmol/L. Moreover, smartphone-based RGB sensing of MT was successfully developed for rapid visualization and portable processing. More broadly, novel insights into the preparation of carbon dots with sensitive fluorescence sensing properties were presented, promising for future considerations.

SERS Immunoassay Based on an Enzyme-Catalyzed Cascade Reaction and Metal-Organic Framework/Alkaline Phosphatase for Ultrasensitive Detection of Adenosine Triphosphate.

Herein, an adenosine triphosphate (ATP)-induced enzyme-catalyzed cascade reaction system based on metal-organic framework/alkaline phosphatase (MOF/ALP) nanocomposites was designed to establish a surface-enhanced Raman spectroscopy (SERS) biosensor for use in rapid, sensitive ATP detection. Numerous ALP molecules were first encapsulated using ZIF-90 to temporarily deactivate the enzyme activity, similar to a lock. Au nanostars (AuNSs), as SERS-enhancing substrates, were combined with o-phenylenediamine (OPD) to form AuNSs@OPD, which could significantly improve the Raman signal of OPD. When the target ATP interacted with the MOF/ALP nanocomposites, ATP could act as a key to open the MOF structure, releasing ALP, which should further catalyze the conversion of OPD to oxOPD with the aid of ascorbic acid 2-phosphate. Therefore, with the increasing concentrations of ATP, more ALP was released to catalyze the conversion of OPD, resulting in the reduced intensity of the Raman peak at 1262 cm-1, corresponding to the level of OPD. Based on this principle, the ATP-induced enzyme-catalyzed cascade reaction SERS biosensor enabled the ultrasensitive detection of ATP, with a low detection limit of 0.075 pM. Consequently, this study provides a novel strategy for use in the ultrasensitive, rapid detection of ATP, which displays considerable potential for application in the fields of biomedicine and disease diagnosis.

Nanocluster-agminated amorphous cobalt nanofilms for highly selective electroreduction of nitrate to ammonia.

Developing highly-efficient electrocatalysts for the nitrate reduction reaction (NITRR) is a persistent challenge. Here, we present the successful synthesis of 14 amorphous/low crystallinity metal nanofilms on three-dimensional carbon fibers (M-NFs/CP), including Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Ag, In, Sn, Pb, Au, or Bi, using rapid thermal evaporation. Among these samples, our study identifies the amorphous Co nanofilm with fine agglomerated Co clusters as the optimal electrocatalyst for NITRR in a neutral medium. The resulting Co-NFs/CP exhibits a remarkable Faradaic efficiency (FENH3) of 91.15 % at - 0.9 V vs RHE, surpassing commercial Co foil (39 %) and Co powder (20 %), despite sharing the same metal composition. Furthermore, during the electrochemical NITRR, the key intermediates on the surface of the Co-NFs/CP catalyst were detected by in situ Fourier-transform infrared (FTIR) spectroscopy, and the possible reaction ways were probed by Density functional theory (DFT) calculations. Theoretical calculations illustrate that the abundant low-coordinate Co atoms of Co-NFs/CP could enhances the adsorption of *NO3 intermediates compared to crystalline Co. Additionally, the amorphous Co structure lowers the energy barrier for the rate-determining step (*NH2→*NH3). This work opens a new avenue for the controllable synthesis of amorphous/low crystallinity metal nano-catalysts for various electrocatalysis reaction applications.

Review on Electrocatalytic Coreduction of Carbon Dioxide and Nitrogenous Species for Urea Synthesis.

The electrochemical coreduction of carbon dioxide (CO2) and nitrogenous species (such as NO3-, NO2-, N2, and NO) for urea synthesis under ambient conditions provides a promising solution to realize carbon/nitrogen neutrality and mitigate environmental pollution. Although an increasing number of studies have made some breakthroughs in electrochemical urea synthesis, the unsatisfactory Faradaic efficiency, low urea yield rate, and ambiguous C-N coupling reaction mechanisms remain the major obstacles to its large-scale applications. In this review, we present the recent progress on electrochemical urea synthesis based on CO2 and nitrogenous species in aqueous solutions under ambient conditions, providing useful guidance and discussion on the rational design of metal nanocatalyst, the understanding of the C-N coupling reaction mechanism, and existing challenges and prospects for electrochemical urea synthesis. We hope that this review can stimulate more insights and inspiration toward the development of electrocatalytic urea synthesis technology.

Cooperative Cationic and Anionic Redox Reactions in Ultrathin Polyvalent Metal Selenide Nanoribbons for High-Performance Electrochemical Magnesium-Ion Storage.

Rechargeable magnesium batteries (RMBs) are considered as potential energy storage devices due to their high volumetric specific capacity, good safety, as well as source abundance. Despite extensive efforts devoted to constructing an efficient magnesium battery system, the sluggish Mg2+ diffusion in conventional cathode materials often leads to slow rate kinetics, low capacity, and poor cycling lifespan. Although transition metal selenides with soft anion frameworks have attracted extensive attention, their Mg2+ storage mechanism still needs to be clarified. Herein, we demonstrate that the ultrathin CoSe2 nanoribbons can be used as a robust cathode material for RMBs and reveal a novel Mg2+ storage mechanism based on cooperative cationic (Co) and anionic (Se) redox processes via systematic ex-situ characterizations. Compared to other metal selenide cathodes based on conversion reactions of solely metal cations, the cooperative cationic-anionic redox reactions of the CoSe2 cathode contribute to obtaining an enhanced specific capacity and boosted electrochemical kinetics. Moreover, on one hand, the ultrathin nanoribbon structure enables effective contact between the electrode material and electrolyte and on the other hand significantly reduces the length and time consumption of Mg2+ diffusion, leading to dominated surface-driven capacitance-controlled Mg2+ storage behavior and rapid Mg2+ storage kinetics. As a result, the ultrathin CoSe2 nanoribbon cathode exhibits a reversible discharge capacity of ∼130 mAh g-1 at 100 mA g-1, good rate capability (116 mAh g-1 at 300 mA g-1), and long cyclability over 600 cycles. This finding confirms the development potentiality of polyvalent metal selenide cathode materials based on a cooperative cationic-anionic redox mechanism for the construction of next-generation multivalent secondary batteries.

Crystalline Modulation Engineering of Ru Nanoclusters for Boosting Ammonia Electrosynthesis from Dinitrogen or Nitrate.

Developing highly efficient nitrogen reduction reaction (NRR) and nitrate reduction reaction (NITRR) electrocatalysts is an ongoing challenge. Herein, we report the in situ growth of ultrafine amorphous Ru nanoclusters with a uniform diameter of ∼1.2 nm on carbon nanotubes as a highly efficient electrocatalyst for both the NRR and the NITRR. The amorphous Ru nanoclusters were prepared via a convenient ambient chelated co-reduction method, in which trisodium citrate as a chelating agent played a key role to form amorphous Ru instead of crystalline Ru. The strong d-π interaction between Ru metal and carbon nanotubes led to the homogeneous distribution and good long-term stability of ultrafine Ru nanoclusters. Compared with crystalline Ru, amorphous Ru nanoclusters with abundant low-coordinate atoms can provide more catalytic sites. The amorphous Ru nanoclusters exhibited an NH3 yield of 10.49 µg·h-1·mgcat.-1 and a FENH3 of 17.48% at -0.2 V vs reversible hydrogen electrode (RHE) for NRR. For the NITRR, an NH3 yield of 145.1 µg·h-1·mgcat.-1 and a FENH3 of 80.62% were also achieved at -0.2 V vs RHE. This work provides new insights into crystalline modulation engineering of metal nanoclusters for electrocatalytic ammonia synthesis.