Model reduction of fractional impedance spectra for time–frequency analysis of batteries, fuel cells, and supercapacitors

Joint time–frequency analysis is an emerging method for interpreting the underlying physics in fuel cells,batteries,and supercapacitors.To increase the reliability of time–frequency analysis,a theoretical correlation between frequency-domain stationary analysis and time-domain transient analysis is urgently required.The present work formularizes a thorough model reduction of fractional impedance spectra for electrochemical energy devices involving not only the model reduction from fractional-order models to integer-order models and from high-to low-order RC circuits but also insight into the evolution of the characteristic time constants during the whole reduction process.The following work has been carried out:(i)the model-reduction theory is addressed for typical Warburg elements and RC circuits based on the continued fraction expansion theory and the response error minimization technique,respectively;(ii)the order effect on the model reduction of typical Warburg elements is quantitatively evaluated by time–frequency analysis;(iii)the results of time–frequency analysis are confirmed to be useful to determine the reduction order in terms of the kinetic information needed to be captured;and(iv)the results of time–frequency analysis are validated for the model reduction of fractional impedance spectra for lithium-ion batteries,supercapacitors,and solid oxide fuel cells.In turn,the numerical validation has demonstrated the powerful function of the joint time–frequency analysis.The thorough model reduction of fractional impedance spectra addressed in the present work not only clarifies the relationship between time-domain transient analysis and frequency-domain stationary analysis but also enhances the reliability of the joint time–frequency analysis for electrochemical energy devices.

Influence of mechanical reduction amount on internal quality of continuous casting billets by thermal and numerical simulation

With establishment of thermal and numerical simulation models,the influence of reduction amount on solidification structure,segregation and shrinkage porosity of continuous casting(CC)billets was investigated.The thermal–mechanical coupled simulation results indicated that with an increase in reduction amount,the temperature in the central area decreases,and the reduction efficiency firstly increases and then decreases,reaching the maximum value at reduction amount of 6 mm.Metallographic analysis showed that increasing the reduction amount is beneficial for the refinement of central solidification structure.Moreover,the internal cracks are more likely to appear at higher reduction efficiency.The X-ray computerized tomography results revealed that a higher reduction amount can significantly reduce the volume fraction and equivalent diameter of the central shrinkage porosities of CC billets and increase the sphericity of them.Simultaneously,the macrosegregation of carbon along the central line is improved as the reduction amount increases;while the reduction amount exceeds 8 mm,the segregation degree will not change any more.

Comprehensive understanding of the thriving electrocatalytic nitrate/nitrite reduction to ammonia under ambient conditions

Ammonia(NH_(3))is a multifunctional compound that is an important feedstock for the agricultural and pharmaceutical industries and attractive energy storage medium.At present,NH_(3)synthesis is highly dependent on the conventional Haber–Bosch process that operates under harsh conditions,which consumes large quantities of fossil fuels and releases a large amount of carbon dioxide.As an alternative,electrosynthesis is a prospective method for producing NH_(3)under normal temperature and pressure conditions.Although electrocatalytic nitrogen reduction to ammonia has attracted considerable attentions,the low solubility of N_(2)and high N≡N cracking energy render the achievements of high NH_(3) yield rate and Faradaic efficiency difficult.Nitrate and nitrite(NO_(x)^(-))are common N-containing pollutants.Due to their high solubilities and low dissociation energy of N=O,NO_(x)^(-)−are ideal raw materials for NH_(3) production.Therefore,electrocatalytic NO_(x)^(-)−reduction to NH_(3)(eNO_(x)RR)is a prospective strategy to simultaneously realise environmental protection and NH_(3) synthesis.This review offers a comprehensive understanding of the thriving eNO_(x)RR under ambient conditions.At first,the popular theory and mechanism of eNO_(x)RR and a summary of the measurement system and evaluation criteria are introduced.Thereafter,various strategies for developing NO_(x)−reduction catalysts are systematically presented and discussed.Finally,the challenges and possible prospects of electrocatalytic NO_(x)^(-1)eduction are outlined to facilitate energy-saving and environmentally friendly large-scale synthesis of NH_(3) in the future.

Copper slag assisted coke reduction of phosphogypsum for sulphur dioxide preparation

The reduction of phosphogypsum(PG)to lime slag and SO_(2)using coke can effectively alleviate the environmental problems caused by PG.However,the PG decomposition temperature remains high and the product yield remains poor.By adding additives,the decomposition temperature can be further reduced and PG decomposition rate and product yield can be improved.However,the use of current additives such as Fe_(2)O_(3)and SiO_(2)brings the problem of increasing economic cost.Therefore,it is proposed to use solid waste copper slag(CS)as a new additive to reduce PG to prepare SO2,which can reduce the cost and meet the environmental benefits at the same time.The effects of proportion,temperature and thermostatic time on PG decomposition are investigated by experimental and kinetic analysis combined with FactSage thermodynamic calculations to optimize the roasting conditions.Finally,the reaction mechanism is proposed.It is found that adding CS to the coke and PG system can increase the rate of PG decomposition and SO_(2)yield while lowering the PG decomposition temperature.For example,when the CS/PG mass ratio increases from 0 to 1,PG decomposition rate increases from 83.38%to 99.35%,SO_(2)yield increases from 78.62%to 96.81%,and PG decomposition temperature decreases from 992.4℃to 949.6℃.The optimal reaction parameters are CS/PG mass ratio of 1,Coke/PG mass ratio of 0.06 at 1100℃for 20 min with 99.35%PG decomposition rate and 96.81%SO_(2) yield.The process proceeds according to the following reactions:2CaSO_(4)+ 0.7C + 0.8Fe_(2)SiO_(4)→0.8Ca_(2)SiO_(4)+ 0.2Ca_(2)Fe_(2)O_(5)+ 0.4Fe_(3)O_(4)+2SO_(2)+ 0.7CO_(2)Finally,a process for decomposing PG with coke and CS is proposed.

A cascade of in situ conversion of bicarbonate to CO_(2) and CO_(2) electroreduction in a flow cell with a Ni-N-S catalyst

Combination of CO_(2) capture using inorganic alkali with subsequently electrochemical conversion of the resultant HCO_(3)^(-)to high-value chemicals is a promising route of low cost and high efficiency.The electrochemical reduction of HCO_(3)^(-)is challenging due to the inaccessible of negatively charged molecular groups to the electrode surface.Herein,we adopt a comprehensive strategy to tackle this challenge,i.e.,cascade of in situ chemical conversion of HCO_(3)^(-)to CO_(2) and CO_(2) electrochemical reduction in a flow cell.With a tailored Ni-N-S single atom catalyst(SACs),where sulfur(S)atoms located in the second shell of Ni center,the CO_(2)electroreduction(CO_(2)ER)to CO is boosted.The experimental results and density functional theory(DFT)calculations reveal that the introduction of S increases the p electron density of N atoms near Ni atom,thereby stabilizing^(*)H over N and boosting the first proton coupled electron transfer process of CO_(2)ER,i.e.,^(*)+e^(-)+^(*)H+^(*)CO_(2)→^(*)COOH.As a result,the obtained catalyst exhibits a high faradaic efficiency(FE_(CO)~98%)and a low overpotential of 425 mV for CO production as well as a superior turnover frequency(TOF)of 47397 h^(-1),outcompeting most of the reported Ni SACs.More importantly,an extremely high FECOof 90%is achieved at 50 mA cm^(-2)in the designed membrane electrode assembly(MEA)cascade electrolyzer fed with liquid bicarbonate.This work not only highlights the significant role of the second coordination on the first coordination shell of the central metal for CO_(2)ER,but also provides an alternative and feasible strategy to realize the electrochemical conversion of HCO_(3)^(-)to high-value chemicals.

Atomically dispersed Mn-Nx catalysts derived from Mn-hexamine coordination frameworks for oxygen reduction reaction

Metal-organic frameworks recently have been burgeoning and used as precursors to obtain various metal-nitrogen-carbon catalysts for oxygen reduction reaction(ORR).Although rarely studied,Mn-N-C is a promising catalyst for ORR due to its weak Fenton reaction activity and strong graphitization catalysis.Here,we developed a facile strategy for anchoring the atomically dispersed nitrogen-coordinated single Mn sites on carbon nanosheets(MnNCS)from an Mn-hexamine coordination framework.The atomically dispersed Mn-N4 sites were dispersed on ultrathin carbon nanosheets with a hierarchically porous structure.The optimized MnNCS displayed an excellent ORR performance in half-cells(0.89 V vs.reversible hydrogen electrode(RHE)in base and 0.76 V vs.RHE in acid in half-wave potential)and Zn-air batteries(233 mW cm^(−2)in peak power density),along with significantly enhanced stability.Density functional theory calculations further corroborated that the Mn-N4-C1_(2)site has favorable adsorption of*OH as the rate-determining step.These findings demonstrate that the metal-hexamine coordination framework can be used as a model system for the rational design of highly active atomic metal catalysts for energy applications.

New process for treating boron-bearing iron ore by flash reduction coupled with magnetic separation

Boron is an important industrial raw material often sourced from minerals containing different compounds that cocrystallize,which makes it difficult to separate the mineral phases through conventional beneficiation.This study proposed a new treatment called flash reduction-melting separation(FRMS)for boron-bearing iron concentrates.In this method,the concentrates were first flash-reduced at the temperature under which the particles melt,and the slag and the reduced iron phases disengaged at the particle scale.Good reduc-tion and melting effects were achieved above 1550℃.The B_(2)O_(3) content in the separated slag was over 18wt%,and the B content in the iron was less than 0.03wt%.The proposed FRMS method was tested to investigate the effects of factors such as ore particle size and tem-perature on the reduction and melting steps with and without pre-reducing the raw concentrate.The mineral phase transformation and morphology evolution in the ore particles during FRMS were also comprehensively analyzed.

Precise regulation of the phase transformation for pyrolusite during the reduction roasting process

The mechanism involved in the phase transformation process of pyrolusite (MnO_(2)) during roasting in a reducing atmosphere was systematically elucidated in this study,with the aim of effectively using low-grade complex manganese ore resources.According to single-factor experiment results,the roasted product with a divalent manganese (Mn^(2+)) distribution rate of 95.30% was obtained at a roasting time of 25 min,a roasting temperature of 700℃,a CO concentration of 20at%,and a total gas volume of 500 mL·min^(-1),in which the manganese was mainly in the form of manganosite (MnO).Scanning electron microscopy and Brunauer–Emmett–Teller theory demonstrated the microstructural evolution of the roasted product and the gradual reduction in the pyrolusite ore from the surface to the core Thermodynamic calculations,X-ray photoelectron spectroscopy,and X-ray diffractometry analyses determined that the phase transformation of pyrolusite followed the order of MnO_(2)→Mn_(2)O_(3)→Mn_(3)O_(4)→MnO phase by phase,and the reduction of manganese oxides in each valence state proceeded simultaneously.

Numerical Study on Reduction in Aerodynamic Drag and Noise of High-Speed Pantograph

Reducing the aerodynamic drag and noise levels of high-speed pantographs is important for promoting environmentally friendly,energy efficient and rapid advances in train technology.Using computational fluid dynamics theory and the K-FWH acoustic equation,a numerical simulation is conducted to investigate the aerodynamic characteristics of high-speed pantographs.A component optimization method is proposed as a possible solution to the problemof aerodynamic drag and noise in high-speed pantographs.The results of the study indicate that the panhead,base and insulator are the main contributors to aerodynamic drag and noise in high-speed pantographs.Therefore,a gradual optimization process is implemented to improve the most significant components that cause aerodynamic drag and noise.By optimizing the cross-sectional shape of the strips and insulators,the drag and noise caused by airflow separation and vortex shedding can be reduced.The aerodynamic drag of insulator with circular cross section and strips with rectangular cross section is the largest.Ellipsifying insulators and optimizing the chamfer angle and height of the windward surface of the strips can improve the aerodynamic performance of the pantograph.In addition,the streamlined fairing attached to the base can eliminate the complex flow and shield the radiated noise.In contrast to the original pantograph design,the improved pantograph shows a 21.1%reduction in aerodynamic drag and a 1.65 dBA reduction in aerodynamic noise.

A post-modification strategy to precisely construct dual-atom sites for oxygen reduction electrocatalysis

Dual-atom catalysts(DACs) afford promising potential for oxygen reduction electrocatalysis due to their high atomic efficiency and high intrinsic activity.However,precise construction of dual-atom sites remains a challenge.In this work,a post-modification strategy is proposed to precisely fabricate DACs for oxygen reduction electrocatalysis.Concretely,a secondary metal precursor is introduced to the primary single-atom sites to introduce direct metal-metal interaction,which ensures the formation of desired atom pair structure during the subsequent pyrolysis process and allows for successful construction of DACs.The as-prepared FeCo-NC DAC exhibits superior oxygen reduction electrocatalytic activity with a half-wave potential of 0,91 V vs.reversible hydrogen electrode.Zn-air batteries equipped with the FeCo-NC DAC demonstrate higher peak power density than those with the Pt/C benchmark.More importantly,this post-modification strategy is demonstrated universal to achieve a variety of dual-atom sites.This work presents an effective synthesis methodology for precise construction of catalytic materials and propels their applications in energy-related devices.

Single-atom catalysts for the electrochemical reduction of carbon dioxide into hydrocarbons and oxygenates

The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.

The photo-decomposition and self-restructuring dynamic equilibrium mechanism of Cu_(2)(OH)_(2)CO_(3)for stable photocatalytic CO_(2)reduction

Developing suitable photocatalysts and understanding their intrinsic catalytic mechanism remain key challenges in the pursuit of highly active,good selective,and long-term stable photocatalytic CO_(2)reduction(PCO_(2)R)systems.Herein,monoclinic Cu_(2)(OH)_(2)CO_(3)is firstly proven to be a new class of photocatalyst,which has excellent catalytic stability and selectivity for PCO_(2)R in the absence of any sacrificial agent and cocatalysts.Based on a Cu_(2)(OH)_(2)^(13)CO_(3)photocatalyst and 13CO_(2)two-sided^(13)C isotopic tracer strategy,and combined with in situ diffused reflectance infrared Fourier transform spectroscopy(DRIFTS)analysis and density functional theory(DFT)calculations,two main CO_(2)transformation routes,and the photo-decomposition and self-restructuring dynamic equilibrium mechanism of Cu_(2)(OH)_(2)CO_(3)are definitely revealed.The PCO_(2)R activity of Cu_(2)(OH)_(2)CO_(3)is comparable to some of state-of-the-art novel photocatalysts.Significantly,the PCO_(2)R properties can be further greatly enhanced by simply combining Cu_(2)(OH)_(2)CO_(3)with typical TiO_(2)to construct composites photocatalyst.The highest CO_(2)and CH_(4)production rates by 7.5 wt%Cu_(2)(OH)_(2)CO_(3)-TiO_(2)reach 16.4μmol g^(-1)h^(-1)and 116.0μmol g^(-1)h^(-1),respectively,which are even higher than that of some of PCO_(2)R systems containing sacrificial agents or precious metals modified photocatalysts.This work provides a better understanding for the PCO_(2)R mechanism at the atomic levels,and also indicates that basic carbonate photocatalysts have broad application potential in the future.

Building Fe atom–cluster composite sites using a site occupation strategy to boost electrochemical oxygen reduction

The high-temperature pyrolysis process for preparing M–N–C single-atom catalyst usually results in high heterogeneity in product structure concurrently contains multiscale metal phases from single atoms(SAs),atomic clusters to nanoparticles.Therefore,understanding the interactions among these components,especially the synergistic effects between single atomic sites and cluster sites,is crucial for improving the oxygen reduction reaction(ORR)activity of M–N–C catalysts.Accordingly,herein,we constructed a model catalyst composed of both atomically dispersed FeN4 SA sites and adjacent Fe clusters through a site occupation strategy.We found that the Fe clusters can optimize the adsorption strength of oxygen reduction intermediates on FeN4 SA sites by introducing electron-withdrawing–OH ligands and decreasing the d-band center of the Fe center.The as-developed catalyst exhibits encouraging ORR activity with halfwave potentials(E1/2)of 0.831 and 0.905 V in acidic and alkaline media,respectively.Moreover,the catalyst also represents excellent durability exceeding that of Fe–N–C SA catalyst.The practical application of Fe(Cd)–CNx catalyst is further validated by its superior activity and stability in a metalair battery device.Our work exhibits the great potential of synergistic effects between multiphase metal species for improvements of singleatom site catalysts.

Rational design of vitamin C/defective carbon van der Waals heterostructure for enhanced activity,durability and storage stability toward oxygen reduction reaction

Metal-free defective carbon materials with abundant active sites have been widely studied as low-cost and efficient oxygen reduction reaction(ORR)electrocatalysts in metal-air batteries.However,the active sites in defective carbon are easily subjected to serious oxidation or hydroxylation during ORR or storage,leading to rapid degradation of activity.Herein,we design a van der Waals heterostructure comprised of vitamin C(VC)and defective carbon(DC)to not only boost the activity but also enhance the durability and storage stability of the DC-VC electrocatalyst.The formation of VC van der Waals between DC and VC is demonstrated to be an effective strategy to protect the defect active sites from oxidation and hydroxylation degradation,thus significantly enhancing the electrochemical durability and storage anti-aging performance.Moreover,the DC-VC van der Waals can reduce the reaction energy barrier to facilitate the ORR.These findings are also confirmed by operando Fourier transform infrared spectroscopy and density functional theory calculations.It is necessary to mention that the preparation of this DC-VC electrocatalyst can be scaled up,and the ORR performance of the largely produced electrocatalyst is demonstrated to be very consistent.Furthermore,the DC-VC-based aluminum-air batteries display very competitive power density with good performance maintenance.

Understanding Bridging Sites and Accelerating Quantum Efficiency for Photocatalytic CO_(2) Reduction

We report a novel double-shelled nanoboxes photocatalyst architecture with tailored interfaces that accelerate quantum efficiency for photocatalytic CO_(2) reduction reaction(CO_(2)RR)via Mo–S bridging bonds sites in S_(v)–In_(2)S_(3)@2H–MoTe_(2).The X-ray absorption near-edge structure shows that the formation of S_(v)–In_(2)S_(3)@2H–MoTe_(2) adjusts the coordination environment via interface engineering and forms Mo–S polarized sites at the interface.The interfacial dynamics and catalytic behavior are clearly revealed by ultrafast femtosecond transient absorption,time-resolved,and in situ diffuse reflectance–Infrared Fourier transform spectroscopy.A tunable electronic structure through steric interaction of Mo–S bridging bonds induces a 1.7-fold enhancement in S_(v)–In_(2)S_(3)@2H–MoTe_(2)(5)photogenerated carrier concentration relative to pristine S_(v)–In_(2)S_(3).Benefiting from lower carrier transport activation energy,an internal quantum efficiency of 94.01%at 380 nm was used for photocatalytic CO_(2)RR.This study proposes a new strategy to design photocatalyst through bridging sites to adjust the selectivity of photocatalytic CO_(2)RR.

Strong synergy between physical and chemical properties:Insight into optimization of atomically dispersed oxygen reduction catalysts

Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.

Porous metal oxides in the role of electrochemical CO_(2) reduction reaction

The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.

Oxygen‑Coordinated Single Mn Sites for Efficient Electrocatalytic Nitrate Reduction to Ammonia

Electrocatalytic nitrate reduction reaction has attracted increasing attention due to its goal of low carbon emission and environmental protection.Here,we report an efficient NitRR catalyst composed of single Mn sites with atomically dispersed oxygen(O)coordination on bacterial cellulose-converted graphitic carbon(Mn-O-C).Evidence of the atomically dispersed Mn-(O-C_(2))_(4)moieties embedding in the exposed basal plane of carbon surface is confirmed by X-ray absorption spectroscopy.As a result,the as-synthesized Mn-O-C catalyst exhibits superior NitRR activity with an NH_(3)yield rate(RNH_(3))of 1476.9±62.6μg h^(−1)cm^(−2)at−0.7 V(vs.reversible hydrogen electrode,RHE)and a faradaic efficiency(FE)of 89.0±3.8%at−0.5 V(vs.RHE)under ambient conditions.Further,when evaluated with a practical flow cell,Mn-O-C shows a high RNH_(3)of 3706.7±552.0μg h^(−1)cm^(−2)at a current density of 100 mA cm−2,2.5 times of that in the H cell.The in situ FT-IR and Raman spectroscopic studies combined with theoretical calculations indicate that the Mn-(O-C_(2))_(4)sites not only effectively inhibit the competitive hydrogen evolution reaction,but also greatly promote the adsorption and activation of nitrate(NO_(3)^(−)),thus boosting both the FE and selectivity of NH_(3)over Mn-(O-C_(2))_(4)sites.

Surface engineering of ZnO electrocatalyst by N doping towards electrochemical CO_(2) reduction

The discovery of efficient,selective,and stable electrocatalysts can be a key point to produce the largescale chemical fuels via electrochemical CO_(2) reduction(ECR).In this study,an earth-abundant and nontoxic ZnO-based electrocatalyst was developed for use in gas-diffusion electrodes(GDE),and the effect of nitrogen(N)doping on the ECR activity of ZnO electrocatalysts was investigated.Initially,a ZnO nanosheet was prepared via the hydrothermal method,and nitridation was performed at different times to control the N-doping content.With an increase in the N-doping content,the morphological properties of the nanosheet changed significantly,namely,the 2D nanosheets transformed into irregularly shaped nanoparticles.Furthermore,the ECR performance of Zn O electrocatalysts with different N-doping content was assessed in 1.0 M KHCO_(3) electrolyte using a gas-diffusion electrode-based ECR cell.While the ECR activity increased after a small amount of N doping,it decreased for higher N doping content.Among them,the N:ZnO-1 h electrocatalysts showed the best CO selectivity,with a faradaic efficiency(FE_(CO))of 92.7%at-0.73 V vs.reversible hydrogen electrode(RHE),which was greater than that of an undoped Zn O electrocatalyst(FE_(CO)of 63.4%at-0.78 V_(RHE)).Also,the N:ZnO-1 h electrocatalyst exhibited outstanding durability for 16 h,with a partial current density of-92.1 mA cm^(-2).This improvement of N:ZnO-1 h electrocatalyst can be explained by density functional theory calculations,demonstrating that this improvement of N:ZnO-1 h electrocatalyst comes from(ⅰ)the optimized active sites lowering the free energy barrier for the rate-determining step(RDS),and(ⅱ)the modification of electronic structure enhancing the electron transfer rate by N doping.

Electrochemical reduction of carbon dioxide to produce formic acid coupled with oxidative conversion of biomass

Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(2) due to its high energy value as estimated by market price per energy unit and wide application in chemical industry.Biomass is the most abundant renewable resource in the natural world.Coupling biomass oxidative conversion with CO_(2)RR driven by renewable electricity would well achieve carbon negativity.In this work,we comprehensively reviewed the current research progress on CO_(2)RR to produce HCOOH and coupled system for conversion of biomass and its derivatives to produce value-added products.Sn-and Bi-based electrocatalysts are discussed for CO_(2)RR with regards to the structure of the catalyst and reaction mechanisms.Electro-oxidation reactions of biomass derived sugars,alcohols,furan aldehydes and even polymeric components of lignocellulose were reviewed as alternatives to replace oxygen evolution reaction(OER)in the conventional electrolysis process.It was recommended that to further improve the efficiency of the coupled system,future work should be focused on the development of more efficient and stable catalysts,careful design of the electrolytic cells for improving the mass transfer and development of environment-friendly processes for recovering the formed formate and biomass oxidation products.