Redistribution Of Electrons Research Articles

Redistribution of Electron Density for Promoting CO2 Conversion Capacity.

There is a need to design substrate-supported catalysts for the heterogeneous fields, especially with large porosity, which can facilitate mass transport. Herein, aiming at enhancing the performance of CO2 fixation, a hollow carbon sphere-supported catalyst of FeNPs/HCS (FeNPs, Fe nanoparticles; HCS, hollow carbon sphere) is facilely designed and fabricated. Excitingly, the experimental and calculation results reveal that FeNPs/HCS displays an ultrahigh activity with almost complete conversions in CO2 cycloaddition, surpassing the performance of FeNPs/CS (CS, carbon sphere); this demonstrates that the HCS plays a key role, which may be attributed to the hollow structure tuning the electron density and enhancing the enrichment of the substrate and CO2, consequently lowering the barrier associated with mass transfer. The work not only provides a novel strategy to construct an efficient catalyst but also proposes, for the first time, an electron redistribution tactic to influence the catalytic process for CO2 cycloaddition.

Nanoporous High Entropy Alloy Al-Pt-Pd-Ru as an Efficient Catalyst for One-Pot Reductive Amination of Nitroarenes.

High entropy alloys (HEAs) are promising heterocatalysts because of their unique physicochemical properties, but research on HEA-catalyzed tandem reactions is lacking. Moreover, limited research on HEAs for molecular transformation has hindered their development. Herein, an unsupported nanoporous HEA Al-Pt-Pd-Ru (HEANPore) prepared using a top-down dealloying method is reported. The Lewis acidity and electron redistribution of the noble metals Pt, Pd, and Ru are identified to be intrinsic of high activity and selectivity of HEANPore in the one-pot reductive amination of nitroarenes. The competitive adsorption of the reactant and corresponding reaction mechanism are investigated using DFT. This study demonstrates the exceptional performance of the HEANPore in tandem reactions, presenting new possibilities for the application of HEAs in the field of catalysis.

Enhanced Basal-Plane Catalytic Activity of MoS2 by Constructing an Electron Bridge for High-Performance Lithium-Sulfur Batteries.

MoS2 is a promising sulfur host material for lithium-sulfur (Li-S) batteries, but its low conductivity and limited active edge sites largely inhibit the catalytic activity toward the conversion of lithium polysulfides (LiPSs). Herein, we propose an electron bridge strategy by combining interlayer structure modification and electronic modulation to activate the basal-plane catalytic activity of MoS2 for the highly efficient catalytic conversion of LiPSs. As validated by experimental characterizations and theoretical calculations, the proposed strategy not only creates a conductive network but also induces delocalized electron redistribution within the MoS2 basal planes, leading to facilitated interfacial charge transfer kinetics and accelerated LiPSs redox kinetics. Because of these advantages, the Li-S batteries assembled with regulated MoS2 demonstrate outstanding electrochemical performance even under practical conditions. This work demonstrates the effectiveness and potential of regulating the intrinsic basal-plane catalytic activity of transition-metal dichalcogenides for Li-S batteries and beyond.

Heterojunction Nanozyme Hydrogels Containing Cu-O-Zn Bonds with Strong Charge Transfer for Accelerated Diabetic Wound Healing.

The complex microenvironment of persistent inflammation and bacterial infection is a major challenge in chronic diabetic wounds. The development of nanozymes capable of efficiently scavenging reactive oxygen species (ROS) is a promising method to promote diabetic wound healing. However, many nanozymes show rather limited antioxidant activity and ROS-dependent antibacterial effects under certain circumstances, further weakening their ability to scavenge ROS. To meet these challenges, electronically regulated bioheterojunction (E-bio-HJ) nanozyme hydrogels derived from metal-organic frameworks (MOFs) were designed and prepared via an interface engineering strategy. Owing to the electron transfer and redistribution effects of the abundant and highly dispersed Cu-O-Zn sites at the heterogeneous interface, the E-bio-HJ nanozymes exhibited catalase (CAT)-like activity with ultrahigh hydrogen peroxide affinity (Km = 25.76 mM) and sustained ROS consumption. In addition, owing to the enhanced interfacial effect of E-bio-HJ and the good biocompatibility and cell adhesion of the methacryloylated gelatin (Gel) hydrogel, the E-bio-HJ gelatin hydrogel (E-bio-HJ/Gel) further reduced inflammation by inducing macrophage transformation to the M2 phenotype, accompanied by excellent antimicrobial properties and enhanced cell migration, angiogenesis, and collagen deposition, which synergistically promoted diabetic wound healing. This highly effective and comprehensive strategy offers a new approach for the rapid healing of diabetic wounds.

Mechanistic insights into facet-dependent catalytic hydrolysis of organophosphate ester by α-MnO2 nanorods

Organophosphate esters (OPEs) are a class of new pollutants with high health and ecological risks, and metal oxide nanoparticles can catalyze their hydrolytic degradation. Yet, the mechanisms dictating how the intrinsic structural properties of metal oxide nanomaterials affect their catalytic activity remain elusive. Herein, we explore the mechanisms through which exposed facets of α-MnO2 nanorods determine their efficiency in catalyzing hydrolysis of 4-nitrophenyl phosphate (pNPP), a model OPE, using in situ spectroscopy and theoretical calculations. Facet-dependent catalytic activity was observed: α-MnO2 nanorods predominantly exposed with the {110} facet exhibited superior adsorption performance and hydrolysis efficiency to those predominantly exposed with the {310} and {200} facets. Surface unsaturated Mn atoms regulate the adsorption affinity of α-MnO2 for pNPP by influencing the coordination complexation strength. This inner-sphere complexation process activates the ester group, promoting the cleavage of the P–O bond and accelerating the hydrolysis reaction. Additionally, facets with higher Lewis acidity induce more pronounced electron redistribution in pNPP, which increases the electrophilicity of the P atom, making it more susceptible to nucleophilic attack and thus facilitating hydrolysis. The findings help predict the environmental fate and risks of OPEs and provide a basis for designing efficient catalytic nanomaterials for their removal.

Asymmetric Polarization Modulation of d-p Hybridization-Enhanced Bidirectional Sulfur Redox Kinetics with Heteronuclear Dual-Atom Catalysts.

Lithium sulfur batteries (LiSBs) represent a highly promising avenue for future energy storage systems, offering high energy density and eco-friendliness. However, the sluggish kinetics of the sulfur redox reaction (SRR) poses a significant challenge to their widespread applications. To tackle this challenge, we have developed an efficient heteronuclear dual-atom catalyst (hetero-DAC) that leverages surface charge polarization to enhance the asymmetric adsorption of sulfur intermediates. This study investigates how asymmetric electronic redistribution of CoFe DACs modulates the d-p orbital hybridization with sulfur intermediates, revealing the mechanisms of moderate adsorption dynamics with enhanced catalytic performance. The dynamic switching between mono and dual adsorption sites, enabled by the heteronuclear polarized configuration, fine-tunes the orbital hybridization, boosting the bidirectional rate-determining steps, that is, the solid-solid conversion of Li2S2 to Li2S and the reverse dissociation of Li2S. Consequently, the thus-designed CoFe DACs cathode delivers impressive rate performance, achieving a high initial specific capacity of 703.9 mA h g-1 at 3 C, with a negligible decay rate of only 0.031% over 1000 cycles, demonstrating sustained long-term cycling stability. This work bridges geometric configurations and electronic structures, elucidating the mechanisms of asymmetric trapping and conversion enabled by hetero-DACs and offering fresh perspectives for catalyst design in LiSBs and beyond.

Constructing Dense CoRu-CoMoO4 Heterointerfaces with Electron Redistribution for Synergistically Boosted Alkaline Electrocatalytic Water Splitting.

Constructing metal alloys/metal oxides heterostructured electrocatalysts with abundant and strongly coupling interfaces is vital yet challenging for practical electrocatalytic water splitting. Herein, CoRu nanoalloys uniformly anchored on CoMoO4 nanosheet heterostructured electrocatalyst (CoRu-CoMoO4/NF) are synthesized via a self-templated strategy by simply annealing of Ru-etched CoMoO4/NF precursor in a reduction atmosphere. The dense and robustly coupled interface not only provides abundant active sites for water splitting but also strengthens the charge transfer efficiency. Furthermore, the theoretical calculations unveil that the strong electronic interaction at CoRu-CoMoO4 interface can induce an interfacial electron redistribution and reduce the energetic barriers for the hydrogen and oxygen intermediates, thereby accelerating the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) kinetics. The resultant catalyst only requires the overpotentials of 49mV for HER and 209mV for OER at 10mAcm-2. Moreover, the constructed CoRu-CoMoO4||CoRu-CoMoO4 two-electrode cell achieves a cell voltage of 1.54V at 10mAcm-2, outperforming the benchmark Pt/C||IrO2. This work explores an avenue for the rational design of heterostructured electrocatalysts with abundant interfaces for practical water-splitting electrocatalysis.

Transition metal ions-chelated COFs derived bifunctional oxygen catalysts for rechargeable Zn-air batteries

Improving energy conversion efficiency and battery cycle stability is an essential goal in energy conversion and storage, while a critical factor in achieving this goal is the design of effective bifunctional catalysts. The covalent organic framework is a new type of high molecular material that can be employed as an ideal template for quantitative chelate metal ions to synthesize highly efficient bifunctional catalysts with high dispersion metal active sites. In this work, the Fe2Ni1/NiFe2O4@NCG bifunctional catalysts are constructed by employing metal-chelated COFs and MA/GO mixture as primary precursors combined with a high-temperature pyrolysis strategy. COFs and MA serve as chelators and spacers to improve the dispersion of metal nanoparticles. The Fe2Ni1/NiFe2O4@NCG composite exhibits a large BET surface area and hierarchical structure with plentiful nanoparticles on the carbon layers. HRTEM proves the coexistence of FeNi and NiFe2O4. The optimal Fe2Ni1/NiFe2O4@NCG-800 composite shows satisfactory catalytic O2 performance, providing a half-wave potential of 0.857 V for ORR and an overpotential of 244 mV for OER. Meanwhile, DFT calculations prove that electron redistribution occurs at the interface between FeNi and NiFe2O4 after combination. The Fe2Ni1/NiFe2O4@NCG-based liquid and solid-state ZABs perform very well, exhibiting large specific capacities (796 mAh·g−1 for aqueous ZAB; 742 mAh·g−1 for solid-state ZAB) and stable charge-discharge cycle performance (300 h for aqueous ZAB; 180 h for solid-state ZAB).

Biphasic 1T/2H-MoS2 Nanosheets In Situ Vertically Anchored on Reduced Graphene Oxide via Covalent Coupling of the Mo-O-C Bond for Enhanced Electrocatalytic Hydrogen Evolution.

Transition-metal dichalcogenides (TMDs) have recently emerged as promising electrocatalysts for the hydrogen evolution reaction owing to their tunable electronic properties. However, TMDs still encounter inherent limitations, including insufficient active sites, poor conductivity, and instability; thus, their performance breakthrough mainly depends on structural optimization in hybridization with a conductive matrix and phase modulation. Herein, a 1T/2H-MoS2/rGO hybrid was rationally fabricated, which is characterized by biphasic 1T/2H-MoS2 nanosheets in situ vertically anchored on reduced graphene oxide (rGO) with strong C-O-Mo covalent coupling. The rGO substrate improves the conductivity and ensures high-dispersed 1T/2H-MoS2 nanosheets to expose plentiful highly active edges. More importantly, the strong heterointerface electrical interaction by the C-O-Mo covalent bond can enhance the charge-transfer efficiency and reinforce structural stability. Furthermore, the integration with the appropriate 2H phase is in favor of stabilization of the metastable 1T phase; thus, the ratio of 1T and 2H was precisely regulated to balance activity and stability. With these advantages, the 1T/2H-MoS2/rGO catalyst presents a satisfactory activity and stability, as confirmed by the relatively low overpotential (268 and 140 mV at 10 mA cm-2) and the small Tafel slope (102 and 86 mV dec-1) in alkaline and acidic media, respectively. The theory calculations disclose that the electronic structure redistribution has been optimized via the strong coupled C-O-Mo heterointerface and phase interface, significantly reducing the adsorption free energy of hydrogen and improving intrinsic activity.

Localized Electron Redistribution in Methanol Molecules over the Sea Urchin-like Tricobalt Tetroxide/Copper Oxide Nanostructures for Fast Hydrogen Release.

Catalytic methanolysis of ammonia borane (NH3BH3) is a prospective technology in the field of hydrogen energy in which hydrogen production and hydrogen storage can be integrated together. The splitting of the O-H bond is identified as the rate-determining step (RDS) in this reaction. Thus, a deep understanding of the relationship between the electronic structure of the catalyst, especially the localized electron density of active sites, and the breaking behaviors of the O-H bond is of extreme importance for the rational design of robust catalysts for the reaction. In this work, sea urchin-like tricobalt tetroxide/copper oxide (Co3O4/CuO) nanostructures with rich oxygen vacancies (Ov) were fabricated by a simple synthetic route. In NH3BH3 methanolysis, the optimal Co3O4/CuO sample exhibited ultrahigh catalytic activity with a turnover frequency (TOF) of 87.5 min-1. Interestingly, when NH3BH3 methanolysis was carried out under visible-light illumination, the TOF further increased to 116.4 min-1, which is the highest TOF value among those of the noble-metal-free catalysts ever documented in the literature. Theoretical calculation results evidenced that the Cu site in the Co3O4/CuO sample was in charge of the adsorption and activation of methanol molecules. Both the Ov and visible-light illumination can help electrons on the Cu site flow to the adsorbed methanol molecule, thus leading to localized electron redistribution of the methanol molecule and the extension of the O-H bond. The cooperation of Ov and visible light makes splitting of the O-H bond easier, which is favorable for fast hydrogen release from NH3BH3 methanolysis. This study helps us to gain an insight into the influence of localized electron redistribution of methanol molecules on the RDS, which conduces to the rational design of highly effective nanocatalysts. Moreover, the coinduction strategy for localized electron redistribution with oxygen vacancy engineering and visible-light illumination opens up a route to boost catalytic activity in NH3BH3 methanolysis.

Synergistic Electronic Interaction in PdCu Alloy/TiO2-NSs for Ambient Efficient Dehydrogenation of Formic Acid.

Palladium-based catalysts are remarkable in endorsing hydrogen (H2) generation through formic acid (HCOOH, FA) dehydrogenation under near-ambient conditions. Hydrogen energy efficiency depends on high-performance catalyst design. In this study, Pd-Cu nanoalloy catalysts with mutable atomic ratios are successfully fabricated on TiO2 nanosheets (TiO2-NSs).The synergistic electronic interactions between Palladium (Pd) and copper (Cu) are revealed through a density of states (DOS) analysis of alloy supported over a mixed valence state of Ti linked to oxygen vacancies (Vo) in TiO2-NSs, Enhanced adsorption of target molecules reveals novel active sites for Formic acid dehydrogenation (FAD), with O─H bond cleavage via HCOO formate intermediate preceding C─H and C─O bond cleavage. Experimental and theoretical research demonstrates that the Pd-Cu/TiO2-NSs (3:7) catalyst d electron redistribution and d-band center shift lower the activation energy for O─H bond cleavage, exhibit superior H2 production than pure Pd and Cu, increasing Pd electron density due to synergistic effects from reactive crystal facets, defects, and strong metal support interactions (SMSI), lowering the activation energy for HCOOH dissociation step, generating carbon dioxide (CO2) and H2 with a unprecedented high turnover frequency (TOF) of 6268 molH2.h-1.molPd-1 at 303K with activation energy (Ea) of 15 KJ mol-1. This attempt models an efficient HCOOH-to-hydrogen catalyst.

FeN4S1 Single-Atom Sites Anchored on Three-Dimensional Porous Carbon for Highly Efficient and Durable Oxygen Electrocatalysis.

Precisely designing asymmetric active centers and exploring their electronic regulation effects to prepare efficient bifunctional single-atom catalysts (SACs) is important for boosting the practical applications of zinc-air batteries (ZABs). Herein, an effective strategy has been developed by introducing an axial S atom to the FeN4 active center, simultaneously assisted by pyrolyzing the graphene oxide (GO) sheathed zeolitic-imidazolate framework-8 (ZIF8) composite and constructing a three-dimensional (3D) porous framework with abundant FeN4S1 moieties. This structure can accelerate the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics owing to the modulated electronic redistribution and d-band center with a reduced energy barrier. The optimal S-Fe-NC/rGO showcases a lower voltage gap (ΔE) of 0.64 V between both the ORR and OER half-wave potentials at 10 mA cm-2, highlighting the excellent bifunctional activities. The assembled S-Fe-NC/rGO rechargeable liquid ZABs deliver a power density of 154.05 mW·cm-2 and a desirable durability of >900 h. More importantly, the corresponding flexible solid-state ZABs exhibit considerable foldability.

Phosphorus Doped MoO2 Enhanced Pt Catalyst for Methanol Oxidation

AbstractThe sluggish kinetics of methanol oxidation reaction (MOR) required high‐performing catalysts in the development of direct methanol fuel cells. Herein, a phosphorus‐doped MoO2 nanorods‐supported Pt catalyst was proposed which exhibited remarkably enhanced catalytic performance toward MOR in comparison with Pt/MoO2 and commercial Pt/C. Specifically, the Pt/MoO2‐P possessed the highest peak current density of 62.63 mA cm−2, about 1.38 and 2.21 times higher than that of Pt/MoO2 (45.24 mA cm−2) and Pt/C (28.40 mA cm−2), respectively. Meanwhile, the Pt/MoO2‐P possessed high intrinsic activity expressed by specific activity and mass activity, and largely improved catalytic kinetics. Moreover, the chronoamperometry and CO‐stripping testing successfully revealed the superior stability and CO‐poisoning resistance of Pt/MoO2‐P, rendering Pt/MoO2‐P a promising catalyst for MOR. The theoretical calculation revealed the electron redistribution and strong metal‐support interaction among Pt/MoO2‐P catalysts. The greatly enhanced catalytic performance could be attributed to the heteroatom doping engineering, greatly enhancing the conductivity, and inducing electron redistribution, thereby leading to the strong metal‐support interaction and high CO‐anti poisoning ability.

Nickel coated paper electrode constructed by interfacial electrodeposition for biomass upgrading at industrial current density

Substituting the kinetically slow oxygen evolution reaction (OER) with biomass electrooxidation significantly decreases the energy demand of water electrolysis. However, exploring and optimizing efficient electrocatalysts remains a challenge for large−scale production of valuable chemicals and hydrogen. Herein, we have constructed a nickel coated paper electrode (NiCo@Ni/CP) composed of crystalline Ni metal and amorphous NiCo hydroxide nanosheets layers via interfacial electrodeposition on carbon paper (CP) for monosaccharide oxidation reactions (MOR), which achieved a formate yield of 82.4 %. Remarkably, the flow electrolyzer maintained an industrial−grade current density of 1 A cm−2 at 1.70 V with exceptional stability over 100 h, also displaying significant co−generation Faradaic efficiencies of approximately 80.0 % and 97.3 % for formate and hydrogen production, respectively. The superior performance is attributed to the redistribution of electrons at the Ni and amorphous NiCo hydroxide interface, which enhances charge transfer and reactant adsorption by adjusting the d−band center, hence reducing deprotonation and C−C bond cleavage energies of xylose during MOR. This work provides a promising strategy for the design of efficient catalysts for biomass upgrading and the production of hydrogen at high current densities.

Point-defect-induced electronic polarization to enhance H* generation for removal of bisphenol A

Intrinsic point defects in metal core-shell materials can regulate electron redistribution, thereby reducing catalytic energy barriers and enhancing their ORR activity. However, their specific contributions to electron transfer and mass transport pathways remain unclear. In this study, defect-rich hollow OCo@Co3O4 nanoparticles were successfully synthesized using ZIF-67(Co) as a sacrificial template through controlled annealing and internal electric field substitution reactions. High-resolution electron microscopy analysis and density functional theory (DFT) calculations co-revealed the growth mechanism of Co and O vacancies, as well as antisite defects. The formation of oxygen vacancies significantly lowered the energy barrier for Co vacancy formation, playing a crucial bridging role in the development of antisite defects. The electric field polarization induced by Co-O atomic displacement resulted in asymmetric charge distribution, optimizing the adsorption of active hydrogen (H*) and oxygen atoms and facilitating the generation and release of reactive oxygen species (ROS). Electrocatalytic experiments demonstrated that under the combined action of singlet oxygen (1O2) and H*, bisphenol A (BPA) can be efficiently degraded. This study successfully bridges the knowledge gap between atomic defects and advanced electrocatalysis, providing a new perspective and insight for the in-depth analysis of the structure-performance relationship of electrocatalyst materials in the future.

First-principle computational insights on Furan- and Thiophene- functionalized zinc-porphyrins as high performance organic cathodes for electrochemical energy storage systems

Organic electrode materials (OEMs) are increasingly replacing conventional inorganic counterparts in metal ion batteries (MIBs) due to their cost-effectiveness and environmental compatibility. Porphyrin-based materials, particularly metalloporphyrins (M-Porph), have garnered significant attention for electrochemical energy storage systems (EESS) owing to their bipolar electrochemical reactivity, making them suitable as both cathodic and anodic materials. However, the correlation between their structure and performance needs further exploration. This computational study examines the redox properties, thermodynamics, and theoretical performance of Zinc(II)-Porphyrin (Zn-Porph) with furan and thiophene substituents. The redox potential (E°) of Zn-Porph changes by 0.17 V with thiophene substituents instead of furan. Thiophene stabilizes the LUMO by 0.105 eV, indicating enhanced electron affinity and faster electron-accepting processes, while the HOMO shows a 0.085 eV stabilization. Thermodynamic calculations reveal that the reduction process intermediates for Zinc(II)-thiophene-Porph are less stable (ΔΔG° = 0.12 eV) than those for furan, suggesting a more accelerated electrochemical process. Additionally, density of states (DOS) analysis of Zn-T18 shows a non-zero DOS at the Fermi energy, indicating available electronic states for occupancy and highlighting its conductive properties. Upon complexation with PF6¯, the Fermi level shifts, reflecting electronic state redistribution and stabilization. The oxidized form, Zn-T16, retains a non-zero DOS at the Fermi energy despite significant Fermi level shifts, ensuring continued electronic conductivity. These findings underscore the robustness and versatility of Zn-porphyrin cathodes in EESS, demonstrating their potential to meet the demands for efficient, cost-effective, and environmentally friendly energy storage solutions.

Efficient electrocatalytic oxygen evolution enabled by porous Eu-Ni(PO3)2 nanosheet arrays

Phosphorous compounds have garnered significant interest as catalysts for the oxygen evolution reaction (OER). However, their catalytic performance often falls short, limiting their widespread application in electrocatalysis. The objective of this work is to improve the OER performance of nickel metaphosphate (Ni(PO3)2) by incorporating rare-earth europium (Eu). The prepared Eu-Ni(PO3)2 exhibits significant electron redistribution and features porous nanosheet arrays. The optimized Eu-Ni(PO3)2 exhibits outstanding OER activity, with an overpotential of 273 mV at 10 mA/cm, rapid OER kinetics with a Tafel slope of 39.4 mV/dec, and excellent electrochemical stability. These results surpass the performance of Ni(PO3)2, many reported Ni-based catalysts, and even commercial RuO2. Operando Raman spectroscopy reveals that the improvement of OER performance on Eu-Ni(PO3)2 is due to the accelerated formation of surface NiOOH active species and the enhanced interfacial water enrichment during OER. Density functional theory (DFT) calculations further demonstrate that Eu doping induces electronic modulation between the Eu sites and adjacent O-Ni sites, resulting in an optimized thermodynamic pathway with balanced adsorption energies for key oxygen intermediates, thus alleviating thermodynamic limitations during OER.

Control Formation of Furans and Pyrazines Resulting from Dual Glycation Sites in Nα,Nε-Di(1-deoxy-d-xylulos-1-yl)lysine via Elevating Thermal Degradation Temperatures.

Lysine (Lys) glycated by xylose (Xyl) at α-NH2 [Nα(1-deoxy-D-xylulos-1-yl)lysine (Nα-Xyl-Lys ARP)] or ε-NH2 [Nε-(1-deoxy-D-xylulos-1-yl)lysine (Nε-Xyl-Lys ARP)] significantly impacted the thermal degradation pathways of Amadori rearrangement products (ARPs). Nα-Xyl-Lys ARP was found to undergo retro-aldolization on the sugar fragment more readily to form glyoxal/methylglyoxal than Nε-Xyl-Lys ARP. Furans and pyrazines formation during the degradation of the diglycated lysine [Nα,Nε-di(1-deoxy-d-xylulos-1-yl)lysine (Nα,Nε-di-Xyl-Lys ARP)] was delayed at 120 °C relative to Nε-Xyl-Lys ARP. This was attributed to the complex degradation of Nα,Nε-di-Xyl-Lys ARP, which slowed the substantial formation of deoxypentosones and the effective release of Lys. At 140 °C, the dual glycated Nα,Nε-di-Xyl-Lys ARP was more conducive to promoting the redistribution of electrons and facilitating molecular rearrangement. This accelerated the efficient decomposition of dual glycated groups in Nα,Nε-di-Xyl-Lys ARP and enabled glyoxal to actively participate in Strecker degradation. Thus, the production of furans and pyrazines was substantially increased, and the variety of pyrazines was expanded from three types to eight types. An appropriate increase to pH 7.5 effectively avoided the overprotonation of hydroxyl and amino groups (pH 5.5), simultaneously enhancing furans and pyrazines yield while minimizing the formation of pyridines under alkaline conditions.

Hierarchical Flower Array NiCoOOH@CoLa‐LDH Nanosheets for High‐Performance Supercapacitor and Alkaline Zn Battery

AbstractNickel oxyhydroxide based energy storage materials have been largely confined by insufficient exposure of active sites which results in low energy efficiency and poor stability. In order to resolve the problems, hierarchical flower array heterostructure NiCoOOH@CoLa‐LDH (denoted as NC@CL) nanosheets are designed with NiCo oxyhydroxide (NiCoOOH, denoted as NC) being tightly covered on CoLa layered double hydroxide (CoLa‐LDH, denoted as CL) nanosheet. This rational design creates more active sites, enlarges the electrode‐electrolyte contact area, improves electron conductivity, and prevents agglomeration during the cycling charge–discharge processes. Density functional theory calculations and differential charges concurrently illustrate that heterostructure formation optimizes the reaction kinetics and promotes electron redistribution. Benefiting from the heterogeneous structure and rich electro‐active sites caused by NC, NC@CL displays outstanding reversible specific capacitance (3228 F g−1 at 1 A g−1). The aqueous rechargeable alkaline Zn battery NC@CL//Zn exhibits a high capacity of 381.1 mA h g−1 at 0.5 A g−1 and cycling durability (98% capacity retention after cycling at 5 A g−1 for 2000 cycles). The excellent electrochemical performances indicate that NC@CL has great application potential as electrode material for aqueous energy storage device.

Stable Zinc Metal Battery Development: Using Fibrous Zirconia for Rapid Surface Conduction of Zinc Ions With Modified Water Solvation Structure.

The two most critical technical issues in Zn-based batteries, dendrite formation, and hydrogen evolution reaction, can be simultaneously addressed by introducing negatively charged fibrous ZrO2 as a separator. Electron redistribution between ZrO2 and Zn2+ ions renders the ZrO2 surface a preferred adsorption site for Zn2+ ions, making surface conduction the primary ion-transport mode. Surface conduction enables fibrous ZrO2 to exhibit a 6.54 times higher single-Zn-ion conductivity than that of conventional glass fiber, minimizing the concentration gradient of Zn2+ and suppressing dendrite formation. Additionally, strong Zr─O─Zn bonding stabilizes the Zn2+ ions with fewer solvated H2O molecules (≈2), preventing water molecules from approaching the electrode surface, as evidenced by a 58.8% decrease in the hydrogen evolution rate. Consequently, the cycling stability of a fibrous-ZrO2-based Zn/Zn symmetric cell (3000h at 1mAhcm-2 and 5mAcm-2) is approximately ten times greater than that of the conventional variant. Furthermore, a fibrous-ZrO2-based Zn-I2 full cell exhibits a notably high energy density (271.4Whkg-1) as well as a long lifespan (≈5000 cycles) at an ultrahigh current density (4Ag-1).