ABSTRACT
The electrocatalytic nitrate reduction reaction (NITRR) holds great promise for purifying wastewater and producing valuable ammonia (NH3). However, the lack of efficient electrocatalysts has impeded the achievement of highly selective NH3 synthesis from the NITRR. In this study, we report the design and synthesis of two polynuclear Co-cluster-based coordination polymers, {[Co2(TCPPDA)(H2O)5]·(H2O)9(DMF)} and {Co1.5(TCPPDA)[(CH3)2NH2]·(H2O)6(DMF)2} (namely, NJUZ-2 and NJUZ-3), which possess distinct coordination motifs with well-defined porosity, high-density catalytic sites, accessible mass transfer channels, and nanoconfined chemical environments. Benefitting from their intriguing multicore metal-organic coordination framework structures, NJUZ-2 and NJUZ-3 exhibit remarkable catalytic activities for the NITRR. At a potential of -0.8 V (vs. RHE) in an H-type cell, they achieve an optimal Faradaic efficiency of approximately 98.5% and high long-term durability for selective NH3 production. Furthermore, the electrocatalytic performance is well maintained even under strongly acidic conditions. When operated under an industrially relevant current density of 469.9 mA cm-2 in a flow cell, a high NH3 yield rate of up to 3370.6 mmol h-1 g-1cat. was observed at -0.5 V (vs. RHE), which is 20.1-fold higher than that obtained in H-type cells under the same conditions. Extensive experimental analyses, in combination with theoretical computations, reveal that the great enhancement of the NITRR activity is attributed to the preferential adsorption of NO3- and the reduction in energy input required for the hydrogenation of *NO3 and *NO2 intermediates.
ABSTRACT
Aqueous rechargeable magnesium batteries hold immense potential for intrinsically safe, cost-effective, and sustainable energy storage. However, their viability is constrained by a narrow voltage range and suboptimal compatibility between the electrolyte and electrodes. Herein, we introduce an innovative ternary deep eutectic Mg-ion electrolyte composed of MgCl2·6H2O, acetamide, and urea in a precisely balanced 1:1:7 molar ratio. This formulation was optimized by leveraging competitive solvation effects between Mg2+ ions and two organic components. The full batteries based on this ternary eutectic electrolyte, Mn-doped sodium vanadate (Mn-NVO) anode, and copper hexacyanoferrate cathode exhibited an elevated voltage plateau and high rate capability and showcased stable cycling performance. Ex-situ characterizations unveiled the Mg2+ storage mechanism of Mn-NVO involving initial extraction of Na+ followed by subsequent Mg2+ intercalation/deintercalation. Detailed spectroscopic analyses illuminated the formation of a pivotal solid-electrolyte interphase on the anode surface. Moreover, the solid-electrolyte interphase demonstrated a dynamic adsorption/desorption behavior, referred to as the "breathing effect", which substantially mitigated undesired dissolution and side reactions of electrode materials. These findings underscore the crucial role of rational electrolyte design in fostering the development of a favorable solid-electrolyte interphase that can significantly enhance compatibility between electrode materials and electrolytes, thus propelling advancements in aqueous multivalent-ion batteries.
ABSTRACT
Aqueous Zn-I batteries hold great potential for high-safety and sustainable energy storage. However, the iodide shuttling effect and the hydrogen evolution reaction that occur in the aqueous electrolyte remain the main obstacles for their further development. Herein, the design of a cathode/electrolyte mutualistic aqueous (CEMA) Zn-I battery based on the inherent oxidation ability of aqueous trifluoromethanesulfonate ((OTf)- ) electrolyte toward triiodide species is presented. This results in the formation of iodine sediment particles assembled by fine iodine nanocrystals (≈10 nm). An iodine host cathode with high areal iodine loading is realized via a spontaneous absorption process that enriched redox-active iodine and iodide species from aqueous electrolyte onto nanoporous carbon based current collector. By tuning iodide redox process and suppressing competitive hydrogen evolution reaction, the assembled CEMA Zn-I batteries demonstrate a remarkable capacity retention of 76.9% over 1000 cycles at 0.5 mA cm-2 . Moreover, they exhibit a notable rate capability, with a capacity retention of 74.6% when the current density is increased from 0.5 to 5.0 mA cm-2 . This study demonstrates the feasibility of using the oxidation effect to repel redox-active species from the electrolyte to the cathode, paving a new avenue for high-performance aqueous Zn-I batteries.
ABSTRACT
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.
ABSTRACT
Two-dimensional (2D) bismuthene is predicted to possess intriguing physical properties, but its preparation remains challenging due to the high surface energy constraint. Herein, we report a sandwiched epitaxy growth strategy for the controllable preparation of 2D bismuthene between a Cu foil substrate and a h-BN covering layer. The top h-BN layer plays a crucial role in suppressing the structural transformation of bismuthene and compensating for the charge transfer from the bismuthene to the Cu(111) surface. The bismuthene nanoflakes present a superior thermal stability up to 500 °C in air, attributed to the passivation effect of the h-BN layer. Moreover, the bismuthene nanoflakes demonstrate an ultrahigh faradaic efficiency of 96.3% for formate production in the electrochemical CO2 reduction reaction, which is among the highest reported for Bi-based electrocatalysts. This study offers a promising approach to simultaneously synthesize and protect 2D bismuthene nanoflakes, which can be extended to other 2D materials with a high surface energy.
ABSTRACT
Although inhibiting the energy metabolism of tumor cells has become an effective measure to enhance chemotherapy, tumor cells can still escape the lethal effect of chemotherapy by entering a dormancy state with low-energy expenditure. Herein, the glutathione (GSH)-responsive nanoplatform (C-A-D NPs) were constructed to inhibit energy metabolism and lysosomal activity of tumor cells, thereby forcing tumor cells to remain vulnerable to cisplatin. In this system, cisplatin prodrug was reduced to cisplatin by GSH, and D-peptide and apoptozole (Az) were released to inhibit the energy metabolism and autophagy-lysosome pathway of tumor cells. The suppressed autophagy-lysosome pathway prevents tumor cells from entering a low-energy dormancy state, resulting in the loss of resistance to the lethal effect of cisplatin with high-energy expenditure and insufficient energy supply. Such engineered nanoplatform effectively enhances the chemotherapeutic effect of cisplatin by inhibiting intracellular energy metabolism and lysosomal activity, showing great clinical prospects.
Subject(s)
Antineoplastic Agents , Nanoparticles , Cisplatin/pharmacology , Cisplatin/therapeutic use , Drug Resistance, Neoplasm , Cell Line, Tumor , Glutathione/metabolism , Energy Metabolism , Lysosomes/metabolism , Antineoplastic Agents/pharmacology , Antineoplastic Agents/therapeutic use , Antineoplastic Agents/metabolismABSTRACT
Metallic zinc (Zn) is a highly promising anode material for aqueous energy storage systems due to its low redox potential, high theoretical capacity, and low cost. However, rampant dendrites/by-products and torpid Zn2+ transfer kinetics at electrode/electrolyte interface severely threaten the cycling stability, which deteriorate the electrochemical performance of Zn-ion batteries. Herein, an interfacial engineering strategy to construct alkaline earth fluoride modified metal Zn electrodes with long lifespan and high capacity retention is reported. The compact fluoride layer is revealed to guide uniform Zn stripping/plating and accelerate the transfer/diffusion of Zn2+ via Maxwell-Wagner polarization. A series of in situ and ex situ spectroscopic studies verified that the fluoride layer can guide uniform Zn stripping/plating. Electrochemical kinetics analyses reveal that positive effect on the removal of Zn2+ solvation sheath provided by fluoride layer. Meanwhile, this fluoride coating layer can act as a barrier between the Zn electrode and electrolyte, providing a high electrode overpotential toward hydrogen evolution reaction to hold back H2 evolution. Consequently, the fluoride-modified Zn anode exhibited a capacity retention of 88.2% after 4000 cycles under10 A g-1 . This work opens up a new path to interface engineering for propelling the exploration of advanced rechargeable aqueous Zn-ion batteries.
ABSTRACT
The conversion of CO2 to high-value products by renewable energy is a promising approach for realizing carbon neutralization, but the selectivity and efficiency of C2+ products are not satisfying. Herein, we report the controllable preparation of highly ordered mesoporous cobalt oxides with modulated surface states to achieve efficient photothermal water-steam reforming of CO2 to C2 products with high activity and tunable selectivity. Pristine mesoporous Co3O4 exhibited an acetic acid selectivity of 96% with a yield rate of 73.44 µmol g-1 h-1. By rationally modifying mesoporous Co3O4 surface states, mesoporous Co3O4@CoO delivered a radically altered â¼100% ethanol selectivity with a yield rate of 14.85 µmol g-1 h-1. Comprehensive experiments revealed that the pH value could strongly influence the selectivity of C2 products over mesoporous cobalt oxides. Density functional theory verified that reduced surface states and rich oxygen vacancies on surface-modified mesoporous cobalt oxides could facilitate further variation of C2 products from acetic acid to ethanol.
ABSTRACT
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.
ABSTRACT
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 â¼130 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.
ABSTRACT
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.
ABSTRACT
Designing earth-abundant electrocatalysts toward highly efficient CO2 reduction has significant importance to decrease the global emission of greenhouse gas. Herein, we propose an efficient strategy to anchor non-noble metal single atoms on Zr6-cluster-porphyrin framework hollow nanocapsules with well-defined and abundant metal-N4 porphyrin sites for efficient electrochemical CO2 reduction. Among different transition metal single atoms (Mn, Fe, Co, Ni, and Cu), Co single-atom anchored Zr6-cluster-porphyrin framework hollow nanocapsules demonstrated the highest activity and selectivity for CO production. The rich Co-N4 active centers and hierarchical porous structure contribute to enhanced CO2 adsorption capability and moderate binding strength of reaction intermediates, thus facilitating *CO desorption and CO2-to-CO conversion. The Co-anchored nanocapsules maintain high efficiency and well-preserved stability during long-term electrocatalysis tests. Moreover, the Co-anchored nanocapsules exhibit a remarkable solar-to-CO energy conversion efficiency of 12.5% in an integrated solar-driven CO2 reduction/O2 evolution electrolysis system when powered by a custom large-area [Cs0.05(FA0.85MA0.15)0.95]Pb0.9(I0.85Br0.15)3-based perovskite solar cell.
ABSTRACT
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 â¼1.2 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.
ABSTRACT
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.
ABSTRACT
Nanozyme is a collection of nanomaterials with enzyme-like activity but higher environmental tolerance and long-term stability than their natural counterparts. Improving the catalytic activity and expanding the category of nanozymes are prerequisites to complement or even supersede enzymes. However, the development of hydrolytic nanozymes is still challenged by diverse hydrolytic substrates and following complicated mechanisms. Here, two strategies are informed by data to screen and predict catalytic active sites of MOF (metal-organic framework) based hydrolytic nanozymes: (1) to increase the intrinsic activity by finely tuned Lewis acidity of the metal clusters; (2) to improve the density of active sites by shortening the length of ligands. Finally, as-obtained Ce-FMA-MOF-based hydrolytic nanozyme is capable of cleaving phosphate bonds, amide bonds, glycosidic bonds, and even their mixture, biofilms. This work provides a rational methodology to design hydrolytic nanozyme, enriches the diversity of nanozymes, and potentially sheds light on future evolution of enzyme engineering.
Subject(s)
Enzymes/chemistry , Enzymes/metabolism , Nanostructures/chemistry , Biofilms/growth & development , Catalysis , Catalytic Domain , Glycoside Hydrolases/chemistry , Hydrolysis , Ions , Ligands , Metal-Organic Frameworks/chemistry , Metals , Phosphoric Monoester Hydrolases/chemistryABSTRACT
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.
Subject(s)
Arsenic , CatalysisABSTRACT
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.
ABSTRACT
Rechargeable silicon anode lithium ion batteries (SLIBs) have attracted tremendous attention because of their merits, including a high theoretical capacity, low working potential, and abundant natural sources. The past decade has witnessed significant developments in terms of extending the lifespan and maintaining high capacities of SLIBs. However, the detrimental issue of low initial Coulombic efficiency (ICE) toward SLIBs is causing more and more attention in recent years because ICE value is a core index in full battery design that profoundly determines the utilization of active materials and the weight of an assembled battery. Herein, a comprehensive review is presented of recent advances in solutions for improving ICE of SLIBs. From design perspectives, the strategies for boosting ICE of silicon anodes are systematically categorized into several aspects covering structure regulation, prelithiation, interfacial design, binder design, and electrolyte additives. The merits and challenges of various approaches are highlighted and discussed in detail, which provides valuable insights into the rational design and development of state-of-the-art techniques to deal with the deteriorative issue of low ICE of SLIBs. Furthermore, conclusions and future promising research prospects for lifting ICE of SLIBs are proposed at the end of the review.
ABSTRACT
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.
ABSTRACT
Rechargeable aluminum-ion batteries (RAIBs) have attracted increasing attention owing to their high theoretical volumetric capacity, high resource abundance, and good safety performance. However, the existing RAIB systems usually exhibit relatively low specific capacities limited by the cathode materials. In this study, we developed a one-step chemical vapor deposition method to prepare single-crystal orthogonal Nb2O5 nanotubes for serving as high-performance electrode materials for RAIBs, showing a high reversible capability of 556 mA h g-1 at 25 mA g-1 and good thermal endurability at elevated temperatures (50 °C). A combination of a series of detailed ex situ structural characterization studies verified the reversible intercalation/deintercalation of chloroaluminate anions (AlCl4-) into/from the (001) planes of monocrystalline Nb2O5 nanotubes. It also revealed that the nanoarchitecture of Nb2O5 nanotubes with thin tube walls, hollow inner space and a short ion transport distance is conducive to the rapid kinetics of the insertion/extraction process. This work provides a promising route to design high-performance electrode materials based on transition metal compounds for RAIBs via the rational modulation of their structure and morphology.