Special topic on strategies for developing energy-related physical chemistry

Increasing global energy demand and environment issue have pushed us to develop technologies for efficient utiliza- tion of fossil fuels and also seek for renewable energy re- sources. Chemistry plays a crucial role in the acquisition, generation, distribution, and utilization of energy in differ- ent forms although it is not the only contributing subject. Currently, fossil fuels are the primary source to provide the majority of the world＇s energy. While the efficient utiliza- tion of fossil fuels requires deep understanding of the ener- gy transformation processes associated with the breaking and reorganization of chemical bonds, the use of many re- newable energy resources often involves chemical trans- formations with electron transfer. For these reasons, energy chemistry has been recently emerging as a new interdisci- plinary area to address chemistry issues associated with energy technologies.

Hot electron electrochemistry at silver activated by femtosecond laser pulses

A silver microelectrode with a diameter of 30μm in an aqueous K_(2)SO_(4) electrolyte was irradiated with 55 fs and 213 fs laser pulses.This caused the emission of electrons which transiently charged the electrochemical double layer.The two applied pulse durations were significantly shorter than the electron-phonon relaxation time.The laser pulse durations had negligible impact on the emitted charge,which is incompatible with multiphoton emission.On the other hand,the ob-served dependence of emitted charge on laser fluence and electrode potential supports the thermionic emission mechanism.

Advances in selective conversion of carbohydrates into 5-hydroxymethylfurfural

Converting carbohydrates into 5-hydroxymethylfurfural(5-HMF) is an attractive and promising route for value-added utilization of agricultural and forestry biomass resource. As an important platform compound, 5-HMF possesses high active furan structure with hydroxymethyl and aldehyde group for production of various bio-chemicals and materials, meanwhile, which suffer from low stability and poor yield during the industrial biorefinery process. Hence, selective production of 5-HMF with high-yield and low-cost has attracted extensive attention from scientific and industrial researchers. This review sorted and described the latest advanced research on solvent and catalyst system, as well as energy field effect for production of 5-HMF with different feedstock in detail, emphatically discussing the solvent effect and its synergistic effect with other aspects. Besides, the future prospects and challenges for production of 5-HMF from carbohydrates were also presented, which provide a profound insight into industrial 5-HMF process with economic and environmental feature.

Surface-modified Ag@Ru-P25 for photocatalytic CO_(2) conversion with high selectivity over CH_(4) formation at the solid–gas interface

Systematic optimization of the photocatalyst and investigation of the role of each component is important to maximizing catalytic activity and comprehending the photocatalytic conversion of CO_(2) reduction to solar fuels.A surface-modified Ag@Ru-P25 photocatalyst with H_(2)O_(2) treatment was designed in this study to convert CO_(2) and H_(2)O vapor into highly selective CH4.Ru doping followed by Ag nanoparticles(NPs)cocatalyst deposition on P25(TiO_(2))enhances visible light absorption and charge separation,whereas H_(2)O_(2) treatment modifies the surface of the photocatalyst with hydroxyl(–OH)groups and promotes CO_(2) adsorption.High-resonance transmission electron microscopy,X-ray photoelectron spectroscopy,X-ray absorption near-edge structure,and extended X-ray absorption fine structure techniques were used to analyze the surface and chemical composition of the photocatalyst,while thermogravimetric analysis,CO_(2) adsorption isotherm,and temperature programmed desorption study were performed to examine the significance of H_(2)O_(2) treatment in increasing CO_(2) reduction activity.The optimized Ag1.0@Ru1.0-P25 photocatalyst performed excellent CO_(2) reduction activity into CO,CH4,and C2H6 with a~95%selectivity of CH4,where the activity was~135 times higher than that of pristine TiO_(2)(P25).For the first time,this work explored the effect of H_(2)O_(2) treatment on the photocatalyst that dramatically increases CO_(2) reduction activity.

Preliminary discussion on the ignition mechanism of exploding foil initiators igniting boron potassium nitrate

Exploding foil initiator(EFI)is a kind of advanced device for initiating explosives,but its function is unstable when it comes to directly igniting pyrotechnics.To solve the problem,this research aims to reveal the ignition mechanism of EFIs directly igniting pyrotechnics.An oscilloscope,a photon Doppler velocimetry,and a plasma spectrum measurement system were employed to obtain information of electric characteristics,impact pressure,and plasma temperature.The results of the electric characteristics and the impact pressure were inconsistent with ignition results.The only thing that the ignition success tests had in common was that their plasma all had a relatively long period of high-temperature duration(HTD).It eventually concludes that the ignition mechanism in this research is the microconvection heat transfer rather than the shock initiation,which differs from that of exploding foil initiators detonating explosives.Furthermore,the methods for evaluating the ignition success of semiconductor bridge initiators are not entirely applicable to the tests mentioned in this paper.The HTD is the critical parameter for judging the ignition success,and it is influenced by two factors:the late time discharge and the energy of the electric explosion.The longer time of the late time discharge and the more energy of the electric explosion,the easier it is to expand the HTD,which improves the probability of the ignition success.

Permeability and selectivity synergistically enhanced nanofluidic membrane for osmotic energy harvesting

For the porous‐membrane‐based osmotic energy generator,the potential synergistic enhancement mechanism of various key parameters is still controversial,especially because optimizing the trade‐off between permeability and selectivity is still a challenge.Here,to construct a permeability and selectivity synergistically enhanced osmotic energy generator,the twodimensional porous membranes with tunable charge density are prepared by inserting sulfonated polyether sulfone into graphene oxide.Influences of charge density and pore size on the ion transport are explored,and the ionic behaviors in the channel are calculated by numerical simulations.The mechanism of ion transport in the process is studied in depth,and the fundamental principles of energy conversion are revealed.The results demonstrate that charge density and pore size should be matched to construct the optimal ion channel.This collaborative enhancement strategy of permeability and selectivity has significantly improved the output power in osmotic energy generation;compared to the pure graphene oxide membrane,the composite membrane presents almost 20 times improvement.

Ionic Liquid-Enhanced Assembly of Nanomaterials for Highly Stable Flexible Transparent Electrodes

The controlled assembly of nanomaterials has demon-strated significant potential in advancing technological devices.However,achieving highly efficient and low-loss assembly technique for nanomate-rials,enabling the creation of hierarchical structures with distinctive func-tionalities,remains a formidable challenge.Here,we present a method for nanomaterial assembly enhanced by ionic liquids,which enables the fabrication of highly stable,flexible,and transparent electrodes featuring an organized layered structure.The utilization of hydrophobic and non-volatile ionic liquids facilitates the production of stable interfaces with water,effectively preventing the sedimentation of 1D/2D nanomaterials assembled at the interface.Furthermore,the interfacially assembled nanomaterial monolayer exhibits an alternate self-climbing behavior,enabling layer-by-layer transfer and the formation of a well-ordered MXene-wrapped silver nanowire network film.The resulting composite film not only demonstrates exceptional photoelectric performance with a sheet resistance of 9.4Ωsq^(-1) and 93%transmittance,but also showcases remarkable environmental stability and mechanical flexibility.Particularly noteworthy is its application in transparent electromagnetic interference shielding materials and triboelectric nanogenerator devices.This research introduces an innovative approach to manufacture and tailor functional devices based on ordered nanomaterials.

Dilute Aqueous-Aprotic Electrolyte Towards Robust Zn-Ion Hybrid Supercapacitor with High Operation Voltage and Long Lifespan

With the merits of the high energy density of batteries and power density of supercapacitors,the aqueous Zn-ion hybrid supercapacitors emerge as a promising candidate for applications where both rapid energy delivery and moderate energy storage are required.However,the narrow electrochemical window of aqueous electrolytes induces severe side reactions on the Zn metal anode and shortens its lifespan.It also limits the operation voltage and energy density of the Zn-ion hybrid supercapacitors.Using'water in salt'electrolytes can effectively broaden their electrochemical windows,but this is at the expense of high cost,low ionic conductivity,and narrow temperature compatibility,compromising the electrochemical performance of the Zn-ion hybrid supercapacitors.Thus,designing a new electrolyte to balance these factors towards high-performance Zn-ion hybrid supercapacitors is urgent and necessary.We developed a dilute water/acetonitrile electrolyte(0.5 m Zn(CF_(3)SO_(3))_(2)+1 m LiTFSI-H_(2)O/AN)for Zn-ion hybrid supercapacitors,which simultaneously exhibited expanded electrochemical window,decent ionic conductivity,and broad temperature compatibility.In this electrolyte,the hydration shells and hydrogen bonds are significantly modulated by the acetonitrile and TFSI-anions.As a result,a Zn-ion hybrid supercapacitor with such an electrolyte demonstrates a high operating voltage up to 2.2 V and long lifespan beyond 120,000 cycles.

Coupling Sb_(2)WO_(6)microflowers and conductive polypyrrole for efficient potassium storage by enhanced conductivity and K^(+) diffusivity

Although metal oxide compounds are considered as desirable anode materials for potassium-ion batteries(PIBs)due to their high theoretical capacity,the large volume variation remains a key issue in realizing metal oxide anodes with long cycle life and excellent rate property.In this study,polypyrroleencapsulated Sb_(2)WO_(6)(denoted Sb_(2)WO_(6)@PPy)microflowers are synthesized by a one-step hydrothermal method followed by in-situ polymerization and coating by pyrrole.Leveraging the nanosheet-stacked Sb_(2)WO_(6)microflower structure,the improved electronic conductivity,and the architectural protection offered by the PPy coating,Sb_(2)WO_(6)@PPy exhibits boosted potassium storage properties,thereby demonstrating an outstanding rate property of 110.3 m A h g^(-1)at 5 A g^(-1)and delivering a long-period cycling stability with a reversible capacity of 197.2 m A h g^(-1)after 500 cycles at 1 A g^(-1).In addition,the conversion and alloying processes of Sb_(2)WO_(6)@PPy in PIBs with the generation of intermediates,K_(2)WO_(4)and K_(3)Sb,is determined by X-ray photoelectron spectroscopy,transmission electron microscopy,and exsitu X-ray diffraction during potassiation/depotassiation.Density functional theory calculations demonstrate that the robust coupling between PPy and Sb_(2)WO_(6)endues it with a much stronger total density of states and a built-in electric field,thereby increasing the electronic conductivity,and thus effectively reduces the K^(+)diffusion barrier.

Constructed Mott-Schottky Heterostructure Catalyst to Trigger Interface Disturbance and Manipulate Redox Kinetics in Li-O_(2) Battery

Lithium-oxygen batteries(LOBs)with high energy density are a promising advanced energy storage technology.However,the slow cathodic redox kinetics during cycling causes the discharge products to fail to decompose in time,resulting in large polarization and battery failure in a short time.Therefore,a self-supporting interconnected nanosheet array network NiCo_(2)O_(4)/MnO_(2)with a Mott-Schottky heterostructure on titanium paper(TP-NCO/MO)is ingeniously designed as an efficient cathode catalyst material for LOBs.This heterostructure can accelerate electron transfer and influence the charge transfer process during adsorption of intermediate by triggering the interface disturbance at the heterogeneous interface,thus accelerating oxygen reduction and oxygen evolution kinetics and regulating product decomposition,which is expected to solve the above problems.The meticulously designed unique structural advantages enable the TP-NCO/MO cathode catalyst to exhibit an astounding ultra-long cycle life of 800 cycles and an extraordinarily low overpotential of 0.73 V.This study utilizes a simple method to cleverly regulate the morphology of the discharge products by constructing a Mott-Schottky heterostructure,providing important reference for the design of efficient catalysts aimed at optimizing the adsorption of reaction intermediates.

Linear paired electrolysis of furfural to furoic acid at both anode and cathode in a multiple redox mediated system

Implementing a new energy-saving electrochemical synthesis system with high commercial value is a strategy of the sustainable development for upgrading the bulk chemicals preparation technology in the future.Here,we report a multiple redox-mediated linear paired electrolysis system,combining the hydrogen peroxide mediated cathode process with the I2 mediated anode process,and realize the conversion of furfural to furoic acid in both side of the dividedflow cell simultaneously.By reasonably controlling the cathode potential,the undesired water splitting reaction and furfural reduction side reactions are avoided.Under the galvanostatic electrolysis,the two-mediated electrode processes have good compatibility,which reduce the energy consumption by about 22%while improving the electronic efficiency by about 125%.This system provides a green electrochemical synthesis route with commercial prospects.

Quantitative lithium substitution of carboxyl hydrogens in polyacrylic acid binder enables robust SiO electrodes with durable lithium storage stability

The design of advanced binders plays a critical role in stabilizing the cycling performance of large-volume-effect silicon monoxide(SiO)anodes.For the classic polyacrylic acid(PAA)binder,the self-association of-COOH groups in PAA leads to the formation of intramolecular and intermolecular hydrogen bonds,greatly weakening the bonding force of the binder to SiO surface.However,strengthening the binder-material interaction from the perspective of binder molecular regulation poses a significant challenge.Herein,a modified PAA-Li_(x)(0.25≤x≤1)binder with prominent mechanical properties and adhesion strength is specifically synthesized for SiO anodes by quantitatively substituting the carboxylic hydrogen with lithium.The appropriate lithium substitution(x=0.25)not only effectively increases the number of hydrogen bonds between the PAA binder and SiO surface owing to charge repulsion effect between ions,but also guarantees moderate entanglement between PAA-Li_x molecular chains through the ion-dipole interaction.As such,the PAA-Li_(0.25)/SiO electrode exhibits exceptional mechanical properties and the lowest volume change,as well as the optimum cycling(1237.3 mA h g^(-1)after 100cycles at 0.1 C)and rate performance(1000.6 mA h g^(-1)at 1 C),significantly outperforming the electrode using pristine PAA binder.This work paves the way for quantitative regulation of binders at the molecular level.

CAOSA-extracted lignin improves enzymatic hydrolysis of cellulose

The conversion of biomass into sugar platform compounds is very important for the biorefinery industry.Pretreatment is essential to the biomass of the sugar platform,however,the lignin obtained by pretreatment,as a key part of lignocellulose,generally has a passive effect on the enzymatic hydrolysis of cellulose into sugars.In this study,p-TsOH(p-toluenesulfonic acid),DES(Deep eutectic solvent)and CAOSA(cooking with active oxygen and solid alkali)pretreatment ways were used to fraction lignin from bamboo biomass.After CAOSA treatment,the hydrolysis efficiency of the pulp was 95.57%.Moreover,the effect of different treatment methods on lignin properties was studied and the promotion effect of lignin was investigated by adding it to the cellulose enzymatic hydrolysis system.In this work,the results showed that CAOSA-extracted lignin with lower D(1.31-1.25)had a better adsorption effect on the enzyme protein.p-TsOH-extracted lignin with a larger S/G ratio enhanced the inhibition of enzymatic hydrolysis.In addition,the presence of-COOHs in lignin could reduce its inhibitory effect on cellulose saccharification.

Healing the structural defects of spinel MnFe_(2)O_(4) to enhance the electrocatalytic activity for oxygen reduction reaction

Spinel metal oxides containing Mn,Co,or Fe(AB_(2)O_(4),A/B=Mn/Fe/Co)are one of the most promising nonPt electrocatalysts for oxygen reduction reaction(ORR)in alkaline conditions.However,the low conductivity of metal oxides and the poor intrinsic activities of transition metal sites lead to unsatisfactory ORR performance.In this study,eutectic molten salt(EMS)treatment is employed to reconstruct the atomic arrangement of MnFe_(2)O_(4)electrocatalyst as a prototype for enhancing ORR performance.Comprehensive analyses by using XAFS,soft XAS,XPS,and electrochemical methods reveal that the EMS treatment reduces the oxygen vacancies and spinel inverse in MnFe_(2)O_(4)effectively,which improves the electric conductivity and increases the population of more catalytically active Mn^(2+)sites with tetrahedral coordination.Moreover,the enhanced Mn-O interaction after EMS treatment is conducive to the adsorption and activation of O_(2),which promotes the first electron transfer step(generally considered as the ratedetermining step)of the ORR process.As a result,the EMS treated MnFe_(2)O_(4)catalyst delivers a positive shift of 40 mV in the ORR half-wave potential and a two-fold enhanced mass/specific activity.This work provides a convenient approach to manipulate the atomic architecture and local electronic structure of spinel oxides as ORR electrocatalysts and a comprehensive understanding of the structureperformance relationship from the molecular/atomic scale.

High-rate lithium-ion battery performance of a ternary sea urchin-shaped CoNiO_(2)@NiP_(6)Mo_(18)/CNTs composites

Bimetallic oxides are attractive anode materials for lithium-ion batteries(LIBs)due to their large theoretical capacity.However,the low conductivity,short cycle life,and poor rate capability are the bottlenecks for their further applications.To overcome above issues,the basket-like polymolybdate(NiP_(6)Mo_(18))and carbon nanotubes(CNTs)were uniformly embedded on the urchin-shaped CoNiO_(2)nanospheres to yield a ternary composites CoNiO_(2)@NiP_(6)Mo_(18)/CNTs via electrostatic adsorption.The multi-level morphology of urchin spinules accelerates the diffusion rate of Li^(+);CNT improves the conductivity and enhances cycle stability of the material;and heteropoly acid contributes more redox activity centres.Thus,CoNiO_(2)@NiP_(6)Mo_(18)/CNTs as an anode of LIBs exhibits a high initial capacity(1396.7 mA h g^(−1)at 0.1 A g^(−1)),long-term cycling stability(750.2 mA h g^(−1)after 300 cycles),and rate performance(450.3 mA h g^(−1)at 2 A g^(−1)),which are superior to reported metallic oxides anode of LIBs.The density functional theory(DFT)and kinetic mechanism suggest that CoNiO_(2)@NiP_(6)Mo_(18)/CNTs delivers an outstanding pseudocapacitance and rapid Li^(+)diffusion behaviors,which is due to the rich surface area of the urchin-like CoNiO_(2)with the uniform embeddedness of NiP_(6)Mo_(18)and CNTs.This study provides a new idea for optimizing the performance of bimetallic oxides and developing high-rate lithium-ion battery composites.

The exchange interaction between neighboring quantum dots:physics and applications in quantum information processing

Electron spins confined in semiconductor quantum dots(QDs)are one of potential candidates for physical implementation of scalable quantum information processing technologies.Tunnel coupling based inter exchange interaction between QDs is crucial in achieving single-qubit manipulation,two-qubit gate,quantum communication and quantum simulation.This review first provides a theoretical perspective that surveys a general framework,including the Helter−London approach,the Hund−Mulliken approach,and the Hubbard model,to describe the inter exchange interactions between semiconductor quantum dots.An electrical method to control the inter exchange interaction in a realistic device is proposed as well.Then the significant achievements of inter exchange interaction in manipulating single qubits,achieving two-qubit gates,performing quantum communication and quantum simulation are reviewed.The last part is a summary of this review.

Boost the Utilization of Dense FeN_(4) Sites for High-Performance Proton Exchange Membrane Fuel Cells

Iron-nitrogen-carbon(Fe-N-C)catalysts for the oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs)have seriously been hindered by their poor ORR performance of Fe-N-C due to the low active site density(SD)and site utilization.Herein,we reported a melamine-assisted vapor deposition approach to overcome these hindrances.The melamine not only compensates for the loss of nitrogen caused by high-temperature pyrolysis but also effectively etches the carbon substrate,increasing the external surface area and mesoporous porosity of the carbon substrate.These can provide more useful area for subsequent vapor deposition on active sites.The prepared 0.20Mela-FeNC catalyst shows a fourfold higher SD value and site utilization than the FeNC without the treatment of melamine.As a result,0.20Mela-FeNC catalyst exhibits a high ORR activity with a half-wave potential(E_(1/2))of 0.861 V and 12-fold higher ORR mass activity than the FeNC in acidic media.As the cathode in a H_(2)-O_(2)PEMFCs,0.20Mela-FeNC catalyst demonstrates a high peak power density of 1.30 W cm^(-2),outstripping most of the reported Fe-N-C catalysts.The developed melamine-assisted vapor deposition approach for boosting the SD and utilization of Fe-N-C catalysts offers a new insight into high-performance ORR electrocatalysts.

CO_(2) electrolysis to formic acid for carbon neutralization

To avoid carbonate precipitation for CO_(2) electrolysis,developing CO_(2) conversion in an acid electrolyte is viewed as an ultimately challenging technology.In Nature,Xia et al.recently explored a proton-exchange membrane system for reducing CO_(2) to formic acid with a Pb±Pb SO_(4) composite catalyst derived from waste lead-acid batteries based on the lattice carbon activation mechanism.Up to 93%Faradaic efficiency was realized when formic acid was produced by this technology.

Deep learning for determining pure isotropic proton spectra from solidstate spectra

Recently,an article on ^(1)H solid-state NMR spectra was published,in which the authors proposed a deep learning approach to infer the pure isotropic proton NMR spectra obtained at an infinite magic angle spinning(MAS)rate.This approach even allowed to obtain,by far,the best resolved ^(1)H spectra of molecular solids[1](https://doi.org/10.1002/anie.202216607).Deep learning based artificial intelligence is developing rapidly,and its application is deepening.Currently,there are many applications of deep learning in the field of magnetic resonance,such as the reconstruction of the under-sampled multidimensional spectra[2-4],the deconvolution of two-dimensional NMR spectra[5]and noise suppression and weak peak retrial[6],etc.

Recent advances in quantifying the inactive lithium and failure mechanism of Li anodes in rechargeable lithium metal batteries

Lithium metal is considered as the ultimate anode material for the next generation of high-energy density batteries.However,non-uniform lithium dendrite growth,serious electrolyte consumption,and significant volume changes during lithium deposition/stripping processes lead to sustained accumulation of inactive lithium and poor cycling reversibility.Quantifying the formation and evolution of inactive lithium under different conditions and fully evaluating the complex failure modes are the key issues in this challenging field.This article comprehensively reviews recent research progress on the quantification of formation and evolution of inactive lithium detected by different quantitative techniques in rechargeable lithium metal batteries.The key research challenges such as failure mechanism,modification strategies and operando characterization of lithium metal anodes are systematically summarized and prospected.This review provides a new angle of view to understand failure mechanism of lithium metal anodes and inspiration and guidance for the future development of rechargeable lithium metal batteries.