Reduction In Activation Energy Research Articles

Stable Strain State of Single‐Twinned AgPdF Nanoalloys under Formate Oxidation Reaction

Surface reconstruction as common phenomenon during catalysis complicates the prediction and modeling on catalytic activity of the nanoalloy, hence developing a stable structure to be resistant to surface restructuring would provide an ideal prototype for substantial and reliable mechanism analysis. Herein, the single‐twinned structure in inverse AgPdF catalyst is constructed to enhance the catalytic activity and stability for the formate oxidation reaction (FOR). The single‐twinned AgPdF nanoalloy (t‐AgPdF) catalyst exhibits an enhanced peak current density of 4.6 A mgPd−1, a reduced onset potential of 0.44 V, a higher activity retention of 55.7% after 600 cycles, and a longer activity retention time of 55.9 h. Additionally, the t‐AgPdF catalyst presents a higher hydrogen generation rate of 1.11 mL mgPd−1 than that of single‐crystalline AgPd nanoalloy (AgPd) catalyst, and density functional theory calculations reveal that t‐AgPdF(111) surface exhibits a reduced activation energy of 0.59 eV for formate decomposition reaction. Impressively, the t‐AgPdF maintains compressive and tensile strain state along the Σ3 twin boundaries before and after the FOR, in contrast to AgPd. This is the first time to reveal that the nanotwinned structures contribute inverse t‐AgPdF catalysts the catalytic active sites with stable strain state since starting reaction for the FOR.

Cross-interaction of volatiles in co-pyrolysis of spinach and noodles and their impacts on properties of pyrolytic products and pyrolysis kinetics

Noodles and spinach are common staple food and vegetables in kitchen waste and they have distinct compositions. Their co-pyrolysis might induce some cross-interactions in terms of volatiles-volatiles or volatiles-biochar, the influence of which on properties of pyrolytic products was studied herein in co-pyrolysis of noodles and spinach at 600 °C. The results indicated that the abundance of inorganics (contained elements such as K, Ca, Na and Cl) in spinach promoted cracking of volatiles, producing more gases at the expense of bio-oil. The inorganics from spinach also promoted further cracking of volatiles from the noodles in the co-pyrolysis, diminishing production of bio-oil. Additionally, cross-polymerization of the volatiles also occurred in the co-pyrolysis, generating oxygen-rich biochar with lower thermal stability but a much higher hydrophilicity. The in-situ Diffuse Reflection Infrared Fourier Transform Spectra (DRIFTS) measurement showed that the inorganics in spinach catalyzed the cracking of aliphatic structures in biochar and hindered aromatization process, leading to the especially low C content of biochar. The kinetic study showed that the co-pyrolysis of noodles and spinach reduced activation energy for conversion of the feedstock, originating from the cross-interactions among the volatiles and between the volatiles and biochar of different origin.

A modified Lotka–Volterra oscillating chemical scheme for detonation simulation

Modified Lotka–Volterra chemical schemes were developed with the goal of performing numerical simulation of detonation driven by single- and multi-stage heat release profiles. An initiation reaction was added to the original Lotka–Volterra model to create an induction zone, which is an important characteristic of combustion process. The kinetics parameters of the reaction rates were adjusted, so that up to eight peaks of heat release could be generated in the steady detonation reaction zone. The structure of steady detonations driven by modified Lotka–Volterra models were examined in detail. Interestingly, the stability criteria typically employed to characterize detonations, i.e., the reduced activation energy and the χ parameter, do not seem to be applicable for Lotka–Volterra schemes exhibiting multi-stage heat release profiles. The applicability of these multi-step chemical models to unsteady detonation simulation was verified through preliminary results obtained for one- and two-dimensional numerical simulations. Under super-critical detonation initiation by a point-energy source, some Lotka–Volterra schemes led to an unusual behavior with large velocity oscillations at large over-drive but a rather steady propagation at near Chapman–Jouguet velocity. Two-dimensional cellular detonation driven by Lotka–Volterra scheme with two stages of heat release and a high activation energy of the initiation step demonstrates some features which are characteristic of a double cellular structure. The present work constitutes a first step toward the understanding of the features and dynamics of detonation driven by Lotka–Volterra schemes as further work is needed to fully grasp the complex responses induced by multiple stages of heat release on detonation dynamics.

Synergistically induced dual-interfacial interactions in iron-nickel sulfides heterojunction encapsulated by N, S-codoped carbon matrix heightened ion-transport kinetics for sodium-storage

Exploring bimetallic sulfides of diverse metal species with well-defined nanoarchitectures and distinctive interfacial interactions is indispensable for advanced sodium-storage systems in achieving rapid electron/ion transfer kinetics, optimizing structural durability, and enhancing electrochemical energy storage. In this regard, the fabrication of a spindle-like hierarchical hollow nanocage with the dual heterointerfaces was reported utilizing N, S co-doped carbon support encapsulating hollow FeS2/NiS heterojunction (FeS2/NiS@N,S-C) through the critical steps of facile dopamine self-polymerization, followed by hydrolyzation, carbonization and further sulphuration. Benefiting from the great superiorities of superior conductivity, excellent structural robustness, abundant active reaction sites, efficient charge transport pathways, as well as fast ion-migration kinetics bestowed by creating an synergistically induced dual interfacial interaction in the ingenious nanoarchitecture, the FeS2/NiS@N,S-C composites render a significantly optimized comprehensive performance of Na+-storage, yielding a highly competitive capacity of 598.0 mAh g−1 after 600 cycles at 1.0 A g−1, and desirable cycle stability with supernormal rate capability (362.6 mAh g−1 after 1950 cycles at 20.0 A g−1), one of the best performances for FeS2- or NiS based heterojunctions. Meanwhile, the redox mechanism involving initial intercalation reaction and following conversion stage was uncovered detailly by a set of ex-situ experimental characterizations. Theoretical evidences drawn from density functional theory calculations illustrate that the formation of dual heterointerfaces in FeS2/NiS@N,S-C composites enables good conductivity, optimizes Na+ adsorption energy, and reduces activation energy for Na+ migration, which facilitates ion/electron migration and enhances reaction kinetics of the electrode.

Understanding the curing kinetics of boron-based hyperbranched polysiloxane reinforced and toughened epoxy resin by rheology

The curing kinetics of epoxy resin (EP) play an important role in optimizing the final properties of the resin, such as thermal stability, flame retardancy and mechanical properties, etc. However, full understanding of the curing kinetic remains a formidable challenge due to the progressively crosslinked structure and the multi-stage exothermic curing reactions. In this study, a hyperbranched polysiloxane (PBPS) with a Si-O-B backbone, containing reactive hydroxyl and epoxy end groups, is synthesized to facilitate the amine curing of EP. For the first time, the contribution of boron to the curing kinetics of epoxy resin is systematically revealed. The Kamal-Sourour model and the Arrhenius four-parameter model, having good fittings to rheology data, successfully describe the isothermal and non-isothermal curing kinetics of the epoxy-amine system loaded with PBPS, respectively. Acting as a Lewis acid, the boron in PBPS coordinates with epoxy groups, efficiently reducing the induction time of curing of the epoxy-amine system. The reaction rate of the non-catalytic stage is increased with reduced activation energy. Meanwhile, a gentle autocatalytic curing stage is achieved with PBPS. The effect of PBPS on the initial viscosity of EP leads to an increase in the activation energy of the viscous flow stage of the non-isothermal process. The curing behavior determines the final properties of EP. The combined effect of improved curing conditions, which endow EP with high crosslink density, and the flexible segments of PBPS exhibit excellent toughening effects. PBPS cavities can in situ form filament structures, thereby reinforcing and toughening the EP. This systematic study fills the knowledge gap regarding the mechanism of hyperbranched polysiloxane participating in the curing of epoxy resin and its influence on the final properties.

Converting and valorizing heavy metal-laden post-harvest hyperaccumulator (Pteris vittate L.) into biofuel via acid-pretreated pyrolysis and gasification

Not only should post-harvest hyperaccumulators rich in heavy metals (HMs) be properly disposed to avoid secondary HMs pollution, but also they should be valorized to enhance circular economy. This study aimed to characterize how As-hyperaccumulator (Pteris vittate L.) (PV) pretreated with HCl or H3PO4 affected its physicochemical, HMs, decomposition, and volatile characteristics. The HCl-pretreated PV retained its original main components, physical properties, and chemical structures but introduced Cl to carbon chain, induced O loss, increased C content, and removed most minerals, in particular, alkali/alkaline earth metals. The favorable pyrolysis and gasification behaviors of PV were maintained via the HCl-pretreated PV, with the raised and narrowed temperature range of mass loss but with the increased energy demand for the decomposition. Compared with PV (276.74 kJ/mol), 5% HCl-pretreated PV reduced activation energy of its pyrolysis (260.62 kJ/mol). The H3PO4 pretreatment destroyed carbon chain, loaded phosphorus oxygen group, and removed more organics and minerals in PV than did the HCl-pretreated PV. This in turn allowed for an earlier start and finish of devolatilization stage, an easier breaking of potential energy barrier, and improvement of reaction favorability. Unlike the two atmospheres, the acid pretreatments changed the temperature dependency of volatile products during the main reaction-temperature range. The volatile products which released from the pyrolysis and gasification at the temperature of maximum mass loss peak or 350 °C were collected. HCl-pretreated PV reduced the formation of ring-opening products, while H3PO4-pretreated PV emitted more aromatic compounds and selectively generated ketone, such as levoglucanone. More HMs were dissolved with the increased acid concentration, with HMs in HCl-pretreated PV being at a higher leaching concentration than those in the other treatments. H3PO4-pretreated PV retained As, Cd, and Pb at a low leachable rate. The best joint optimization was achieved with the combined settings of 5% HCl-pretreated PV or 10% H3PO4-pretreated PV at 10 °C/min in the N2 atmosphere. Overall, findings provide new insights into how to best manage and valorize post-harvest and HM-laden hyperaccumulators.

Synergistic interactions between sewage sludge, polypropylene, and high-density polyethylene during co-pyrolysis: An investigation based on iso-conversional model-free methods and master plot analysis

Sewage sludge (SS) is a hazardous by-product of wastewater treatment processes that requires careful management for minimal environmental impacts and effective resource recovery. Through thermochemical processes such as pyrolysis, clean energy is recovered from SS in the form of bio-oil, biogas, and biochar. To improve the yield and quality of products, the co-pyrolysis of more than two materials is increasingly gaining interest. Here, the thermal behaviour, kinetics, and synergistic interactions during the co-pyrolysis of SS with polypropylene (PP) and high-density polyethylene (HDPE) were comparatively evaluated with thermogravimetric analysis at different mixing ratios and heat rates. Activation energies and reaction mechanisms were determined through iso-conversional model-free methods and master plot analysis. Evolved gases were monitored with thermogravimetric-mass spectrometry. Increased volatile conversion and degradation rates, and reduced activation energies during co-pyrolysis were mediated by synergistic interactions between H-radicals of PP/HDPE and oxygenated intermediates of SS. Contrary to the pyrolysis of SS, PP and HDPE, the co-pyrolysis processes are predominantly diffusion-controlled. Insights into the co-pyrolysis processes of SS/PP and SS/HDPE gained from this work provide the theoretical support for subsequent investigation, facilitate design of waste-to-energy reactor, and aid the adoption of the technology to harness the bioenergy potential of the feedstocks.

Challenges in unconventional catalysis

Catalysis science and technology increased efforts recently to progress beyond conventional "thermal" catalysis and face the challenges of net-zero emissions and electrification of production. Nevertheless, a better gaps and opportunities analysis is necessary. This review analyses four emerging areas of unconventional or less-conventional catalysis which share the common aspect of using directly renewable energy sources: (i) plasma catalysis, (ii) catalysis for flow chemistry and process intensification, (iii) application of electromagnetic (EM) fields to modulate catalytic activity and (iv) nanoscale generation at the catalyst interface of a strong local EM by plasmonic effect. Plasma catalysis has demonstrated synergistic effects, where the outcome is higher than the sum of both processes alone. Still, the underlying mechanisms are complex, and synergy is not always obtained. There is a crucial need for a better understanding to (i) design catalysts tailored to the plasma environment, (ii) design plasma reactors with optimal transport of plasma species to the catalyst surface, and (iii) tune the plasma conditions so they work in optimal synergy with the catalyst. Microfluidic reactors (flow chemistry) is another emerging sector leading to the intensification of catalytic syntheses, particularly in organic chemistry. New unconventional catalysts must be designed to exploit in full the novel possibilities. With a focus on (a) continuous-flow photocatalysis, (b) electrochemical flow catalysis, (c) microwave flow catalysis and (d) ultrasound flow activation, a series of examples are discussed, with also indications on scale-up and process industrialisation. The third area discussed regards the effect on catalytic performances of applying oriented EM fields spanning several orders of magnitude. Under well-defined conditions, gas breakdown and, in some cases, plasma formation generates activated gas phase species. The EM field-driven chemical conversion processes depend further on structured electric/magnetic catalysts, which shape the EM field in strength and direction. Different effects influencing chemical conversion have been reported, including reduced activation energy, surface charging, hot spot generation, and selective local heating. The last topic discussed is complementary to the third, focusing on the possibility of tuning the photo- and electro-catalytic properties by creating a strong localised electrical field with a plasmonic effect. The novel possibilities of hot carriers generated by the plasmonic effect are also discussed. This review thus aims to stimulate the reader to make new, creative catalysis to address the challenges of reaching a carbon-neutral world.

Design of metal-organic frameworks for improving pseudo-solid-state magnesium-ion electrolytes: Open metal sites, isoreticular expansion, and framework topology

The design criteria for metal-organic frameworks (MOFs) have been established by evaluating the relationship between their key characteristics and magnesium-ion conductivity based on three types of secondary building blocks (Zn4O(CO2)6: MOF-5 and MOF-177; Cu2(CO2)4: MOF-199, MOF-143, MOF-14, and MOF-399; Cu2O2(CO2)2: Cu-MOF-74) to achieve pseudo-solid-state magnesium-ion conduction. We found that open-metal sites and channel layouts play a pivotal role in promoting magnesium-ion transport dynamics at reduced activation energy, transforming MOF scaffolds into ionic-channel analogs. X-ray absorption spectroscopy combined with Raman and Fourier-transform infrared spectroscopy predicted the chemical environment, solvents, and anions that occupied coordinatively unsaturated metal sites. The chemical compositions of electrolytes determined by 1H-NMR (nuclear magnetic resonance) and organic elemental analysis confirmed that isoreticular expansion increases the molar percentage of charge carriers, providing high conductivity. The current research systematically reveals the impacts of different MOF characteristics on ionic conduction performance, paving the way for the construction of a new class of fast and selective multivalent-ion pseudo-solid electrolytes.

Wet synthesis, characterization of goethite nanoparticles and its application in catalytic pyrolysis of palm kernel shell in TGA

Catalytic pyrolysis of biomass is a suitable means of obtaining high-yield bio-oil with reduced activation energy and char content. Goethite nanoparticles were synthesized via coprecipitation of FeCl2.4H2O and NaHCO3. TGA purged with N2 was used to study goethite’s catalytic effect on the thermal degradation of PKS. The obtained particles were characterized via instrumental analysis using BET, TEM, SEAD, and XRD gave multipoint SA of 309 m2/g & 0.276 cc/g; 18.33 nm; rings occurring at (101), (111), (021); and crystallinity of 51.51% with average size of 9.16 nm respectively. Their morphology was circular and needle-like shape. Its average crystallite size was 9.16 nm with a crystallinity of 51.51%. The 62.10% Fe in goethite was a suitable factor for its application as a catalyst in the thermal decomposition of PKS. The average Ea for uncatalyzed PKS were 53.45, 44.95, 47.09, 49.05 and 70.63 kJ/mol for order n =1, 0.30, 0.50, 0.67 and 2.00 respectively at the α of 0.2 while the average Ea for catalyzed PKS were 19.17, -17.70, 10.27, 12.64 and 52.69 kJ/mol for same order sequence at α of 0.71 using Coats–Redfern kinetics model. The goethite nanoparticles reduced Ea with higher α due to its special physicochemical properties.

Cold sintering process assisted sintering for 8YSZ ceramic: A way of achieving high density and electrical conductivity at a reduced sintering temperature

Yttria-stabilized zirconia (YSZ) is a well-studied and practically applied electrolyte for solid oxide fuel cells (SOFC), but the high sintering temperature causes some problems. In this work, 8 mol% yttria-stabilized zirconia (8YSZ) ceramics were prepared by a cold sintering process (CSP) technique associated with post-heat-treatment (PHT). The CSP was beneficial for getting high initial density for the green bulk, while the PHT could further improve the bulk density of the 8YSZ ceramics at a reduced sintering temperature. Electrochemical impedance spectra showed that the electrical conductivity was 0.060 S/cm at 850 °C for the 8YSZ ceramic prepared by CSP-PHT at 1300 °C, about twice of that prepared by CS. The improved electrical conductivity was attributed to the high density and the reduced activation energy relevant to refined grain size and increased bulk density. Our study demonstrates that the CSP-PHT is a promising technique for preparation of high-dense YSZ ceramics with improved electrical conductivity at a reduced sintering temperature.

Tailoring the electronic states of Pt by atomic layer deposition of Al2O3 for enhanced CO oxidation performance: Experimental and theoretical investigations

Herein, atomic layer deposition (ALD)-Al2O3 films were applied as a medium to modulate the electronic states of the supported Pt. Based on the sacrificial template of ZIF-67, the ternary Co3O4/Pt/Al2O3 catalyst exhibited better performance in catalytic CO oxidation than the binary Co3O4/Pt catalyst. Both experimental and calculation results indicate the existence of charge transport between the Pt and the ALD-Al2O3 films, leading to electron-rich Pt, enhanced O2 affinity, and reduced activation energy. Interestingly, the oxidation resistance of Pt nanoparticles was visualized when annealing Co3O4/Pt/Al2O3 catalyst at high temperatures. Mechanism studies indicate the typical LH mechanism occurred in CO oxidation, showing that the co-adsorbed CO and O2 could be converted to carbonate-type *OCOO intermediates via low energy barriers. At low temperatures, CO2 was mainly produced by the lattice oxygen-mediated M-vK mechanism based on isotope labeling experiments. Our findings provide an alternative way to regulate the electronic states of noble metals by the ALD technique.

Construction of an Artificial Interfacial Layer with Porous Structure toward Stable Zinc‐Metal Anodes

Aqueous zinc‐ion batteries possess great potential in stationary energy storage devices. Nevertheless, the occurrence of zinc dendrite growth and hydrogen evolution reaction severely hinders the utilization efficiency and service life of zinc‐metal anodes. Herein, an in situ etching strategy is proposed to construct an interfacial layer with porous structure on the surface of zinc foil under the assistance of tartaric acid (denoted as TA@Zn). The optimized anode surface is beneficial to not only achieve uniform Zn deposition behavior due to the low nucleation overpotential, but also enhance the interfacial reaction kinetics due to the reduced activation energy barrier. As expected, the TA@Zn‐based symmetric cell delivers small voltage hysteresis and superior stability for 5000 h at the current density of 1 mA cm−2. Moreover, the TA@Zn|NH4V4O10cell also exhibits high specific capacity and long‐term cycling stability.

Metal‐organic framework stabilizes Cu7S4‐wrapped Cu2O heterostructure for photothermal‐promoted methanol/water reforming into hydrogen

AbstractTo realize highly efficient in situ release of hydrogen energy from methanol reforming at lower operation temperature, the introduction of solar energy can effectively activate the methanol and significantly reduce activation energy of reaction. Herein, the hierarchical integration of photoactive Cu2O/Cu7S4 core‐shell nanospheres stabilized by MIL‐101(Cr) support for H2 evolution from photothermal‐driven aqueous phase reforming of methanol afforded nearly sixfold enhanced performance compared with thermocatalytic process. Impressively, the photothermal effect conferred the Cu2O/Cu7S4@MIL‐101(Cr) with unprecedented activity at low temperature subside to 100°C and accelerated the activation of water and methanol with distinctly decreased activation energy from 103.9 to 66.6 kJ·mol−1. Meanwhile, the enhanced catalyst stability and facilitated charge separation between Cu2O/Cu7S4 and MIL‐101(Cr) also contribute to the extraordinary photothermal‐enhanced H2 evolution with an overall turnover number of up to 14,266 in 60 h (apparent quantum efficiency of 25.08% at 365 nm), almost 10,000 times higher than that of Cu2O/Cu7S4.

Nitrogen‐Doped Electrocatalysts, and Photocatalyst in Water Splitting: Effects, and Doping Protocols

AbstractWater splitting has been widely studied since the reaction affords hydrogen as an energetic pollutant‐free fuel from the most abundant molecule. Electrolysis, and photolysis of water are reliable pathways for hydrogen generation in green conditions, in which a catalyst is in charge of the transformation, and manipulation of its structure predominantly impresses the reaction rate. In this review, we concentrated on the impacts of nitrogen doping on the catalyst activity in electrocatalytic and photocatalytic water splitting. Increasing conductivity, formation of new edges for evolution reaction, elevating surface area by prohibition from the aggregation of the support, enhancing transition metal deposition into the support, reducing activation energy of proton evolution, shrinking bandgap of photocatalysts, increasing light harvesting, and retarding charges recombination are the most significant results of the nitrogen doping on the catalysts. Moreover, the syntheses procedures were summarized herein to provide a comprehensive view for the nitrogen doping process.

Properties of AB5 type hydrogen storage alloy after α-AlH3 alloying

AB5 type hydrogen storage alloys have been widely used in Ni-MH batteries due to their high electrochemical capacity, excellent rate performance, and low pollution. However, the high activation difficulty limited their development in the solid-state hydrogen storage field. Mechanical alloying to synthesize composites is an effective way to reduce activation energy. In this paper, the structure and hydrogen storage properties of the LaNi5+nAlH3 (n = 0, 1, 3 wt.%) composites were investigated. The results show that with the incremental of AlH3 alloying content, the lattice constant a, b, and c and the volume (V) of the LaNi5 unit cell tend to increase, the hydrogen absorption platform pressure of the composite material gradually decreased, and the hydrogen release platform pressure gradually increased. It resulted in a reduction in the hysteresis factor (Hf) of the composite from 0.66 to 0.35. This will reduce energy waste during energy conversion. In addition, the activation property of the alloy was improved after AlH3 alloying. This will facilitate the application of AB5 type hydrogen storage alloys.

Oxygen Vacancies Engineering in Thick Semiconductor Films via Deep Ultraviolet Photoactivation for Selective and Sensitive Gas Sensing

AbstractRoom‐temperature detection of volatile organic compounds in particle‐per‐billion concentrations is critical for the development of wearable and distributed sensor networks. However, sensitivity and selectivity are limited at low operating temperatures. Here, a strategy is proposed to substantially improve the performance of semiconductor sensors. Tunable oxygen vacancies in thick 3D networks of metal oxide nanoparticles are engineered using deep ultraviolet photoactivation. High selectivity and sensitivity are achieved by optimizing the electronic structure and surface activity while preserving the 3D morphology. Cross‐sectional depth analysis reveals oxygen vacancies present at various depths (≈24% at a depth of 1.13 µm), with a uniform distribution throughout the thick films. This results in ≈58% increase in the sensitivity of ZnO to 20‐ppb ethanol at room temperature while ≈51% and 64% decrease in the response and recovery times, respectively. At an operating temperature of 150 °C, oxygen‐vacant nanostructures achieve a lower limit of detection of 2 ppb. Density functional theory analysis shows that inducing oxygen vacancies reduces activation energy for ethanol adsorption and dissociation, leading to improved sensing performance. This scalable approach has the potential for designing low‐power wearable chemical and bio‐sensors and tuning the activity and band structure of porous, thick oxide films for multiple applications.

Promoting the electrocatalytic oxygen evolution reaction on NiCo2O4 with infrared-thermal effect: A strategy to utilize the infrared solar energy to reduce activation energy during water splitting

Utilization of the infrared (IR) solar energy remains a challenging task for traditional photo(electro)catalysis. Taking advantage of the IR-thermal effect to facilitate sluggish electrocatalytic reactions emerges as a promising way to utilize the IR band of the solar spectrum. In this work, nickel foam (NF) supported NiCo2O4 nanoneedles (NF/NiCo2O4 NNs) were prepared to promote the oxygen evolution reaction (OER) via the IR-thermal effect, with the NF/NiCo2O4 NNs acting as both the IR absorbing antennae and the OER active anode. The potential required to deliver a current density of 200 mA cm−2 is negatively shifted from 1.618 V in the dark to 1.578 V under IR irradiation, and the Tafel slope is also decreased from 106 to 89 mV dec−1. We demonstrate that the enhancement of OER activity is due to the localized temperature rise under IR irradiation. We measured the electrochemical activation energy of OER on NF/NiCo2O4 with and without IR irradiation, and the results reveal that IR irradiation reduces the kinetic energy barrier of the OER by IR-thermal effect and then facilitates OER kinetics. This work highlights a new approach to utilizing the IR portion of the sunlight to produce renewable hydrogen energy via water splitting.

Ultrathin CuF2‐Rich Solid‐Electrolyte Interphase Induced by Cation‐Tailored Double Electrical Layer toward Durable Sodium Storage

AbstractSolid‐electrolyte interphase (SEI) seriously affects battery's cycling life, especially for high‐capacity anode due to excessive electrolyte decomposition from particle fracture. Herein, we report an ultrathin SEI (3–4 nm) induced by Cu+‐tailored double electrical layer (EDL) to suppress electrolyte consumption and enhance cycling stability of CuS anode in sodium‐ion batteries. Unique EDL with SO3CF3‐Cu complex absorbing on CuS in NaSO3CF3/diglyme electrolyte is demonstrated by in situ surface‐enhanced Raman, Cyro‐TEM and theoretical calculation, in which SO3CF3‐Cu could be reduced to CuF2‐rich SEI. Dispersed CuF2 and F‐containing compound can provide good interfacial contact for formation of ultrathin and stable SEI film to minimize electrolyte consumption and reduce activation energy of Na+ transport. As a result, the modified CuS delivers high capacity of 402.8 mAh g−1 after 7000 cycles without capacity decay. The insights of SEI construction pave a way for high‐stability electrode.

Ultrathin CuF2 -Rich Solid-Electrolyte Interphase Induced by Cation-Tailored Double Electrical Layer toward Durable Sodium Storage.

Solid-electrolyte interphase (SEI) seriously affects battery's cycling life, especially for high-capacity anode due to excessive electrolyte decomposition from particle fracture. Herein, we report an ultrathin SEI (3-4 nm) induced by Cu+ -tailored double electrical layer (EDL) to suppress electrolyte consumption and enhance cycling stability of CuS anode in sodium-ion batteries. Unique EDL with SO3 CF3 -Cu complex absorbing on CuS in NaSO3 CF3 /diglyme electrolyte is demonstrated by in situ surface-enhanced Raman, Cyro-TEM and theoretical calculation, in which SO3 CF3 -Cu could be reduced to CuF2 -rich SEI. Dispersed CuF2 and F-containing compound can provide good interfacial contact for formation of ultrathin and stable SEI film to minimize electrolyte consumption and reduce activation energy of Na+ transport. As a result, the modified CuS delivers high capacity of 402.8 mAh g-1 after 7000 cycles without capacity decay. The insights of SEI construction pave a way for high-stability electrode.