Insights on advanced substrates for controllable fabrication of photoanodes toward efficient and stable photoelectrochemical water splitting

Conversion of solar energy into H_(2) by photoelectrochemical(PEC)water splitting is recognized as an ideal way to address the growing energy crisis and environmental issues.In a typical PEC cell,the construction of photoanodes is crucial to guarantee the high efficiency and stability of PEC reactions,which fundamentally rely on rationally designed semiconductors(as the active materials)and substrates(as the current collectors).In this review work,we start with a brief introduction of the roles of substrates in the PEC process.Then,we provide a systematic overview of representative strategies for the controlled fabrication of photoanodes on rationally designed substrates,including conductive glass,metal,sapphire,silicon,silicon carbide,and flexible substrates.Finally,some prospects concerning the challenges and research directions in this area are proposed.

Role of methoxy and C_(α)-based substituents in electrochemical oxidation mechanisms and bond cleavage selectivity of β-O-4 lignin model compounds

In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl groups, including 2-(2-methoxyphenoxy)-1-phenylethanone, 2-(2-methoxyphenoxy)-1-phenylethanol, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanol, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanol have been selected and their electrochemical properties have been studied experimentally by cyclic voltammetry, and FT-IR spectroelectrochemistry. Combining with electrolysis products distribution analysis and density functional theory calculations, oxidation mechanisms of all six model dimers have been explored. In particular, a total effect from substituents of both para-methoxy(on the aryl ring closing to Cα) and Cα-OH on the oxidation mechanisms has been clearly observed, showing a significant selectivity on the Cα-Cβbond cleavage induced by electrochemical oxidations.

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.

Design method of extractant for liquid-liquid extraction based on elements and chemical bonds

In the petrochemical industry process, the relative volatility between the components to be separated is close to one or the azeotrope that systems are difficult to separate. Liquid-liquid extraction is a common and effective separation method, and selecting an extraction agent is the key to extraction technology research. In this paper, a design method of extractants based on elements and chemical bonds was proposed. A knowledge-based molecular design method was adopted to pre-select elements and chemical bond groups. The molecules were automatically synthesized according to specific combination rules to avoid the problem of “combination explosion” of molecules. The target properties of the extractant were set, and the extractant meeting the requirements was selected by predicting the correlation physical properties of the generated molecules. Based on the separation performance of the extractant in liquid-liquid extraction and the relative importance of each index, the fuzzy comprehensive evaluation membership function was established, the analytic hierarchy process determined the mass ratio of each index, and the consistency test results were passed. The results of case study based on quantum chemical analysis demonstrated that effective determination of extractants for the analysis of benzene-cyclohexane systems. The results unanimously prove that the method has important theoretical significance and application value.

Hydrogen-bonded organic framework modified separator for simultaneously enhancing the safety and electrochemical performance of Ni-rich lithium-ion battery

Nickel-rich layered oxide cathode(LiNi_(x)Co_(y)Mn_(1−x−y)O_(2),x>0.5,NCM)shows substantial potential for applications in longer-range electrical vehicles.However,the rapid capacity decay and serious safety concerns impede its practical viability.This work provides a hydrogen-bonded organic framework(HOF)modification strategy to simultaneously improve the electrochemical performance,thermal stability and incombustibility of separator.Melamine cyanurate(MCA),as a low-cost and reliable flame-retardant HOF,was implemented in the separator modification layer,which can prevent the battery short circuit even at a high temperature.In addition,the supermolecule properties of MCA provide unique physical and chemical microenvironment for regulating ion-transport behavior in electrolyte.The MCA coating layer enabled the nickel-rich layered oxide cathode with a high-capacity retention of 90.3%after 300 cycles at 1.0 C.Collectively,the usage of MCA in lithium-ion batteries(LIBs)affords a simple,low-cost and efficient strategy to improve the security and service life of nickel-rich layered cathodes.

Mechanochemical synthesis of oxygenated alkynyl carbon materials with excellent Hg(Ⅱ) adsorption performance from CaC2 and carbonates

Adsorptive removal of heavy metal ions from wastewater is very important,and the key is the development of efficient sorbents.In this work,oxygenated alkynyl carbon materials(OACMs)were synthesized via mechanochemical reaction of CaC_(2) and a carbonate(CaCO_(3),Na2CO_(3),or NaHCO_(3))at ambient temperature.The resultant OACMs are micro mesoporous carbon nanomaterials with high specific area(>648 m2 g^(-1)),highly crosslinked texture,and rich alkynyl and oxygenated groups.The OACMs exhibit excellent Hg(Ⅱ)adsorption due to the soft acid-soft base interaction between alkynyl and Hg(Ⅱ),and OACM-3 derived from CaC_(2) and NaHCO_(3) has the saturated Hg(Ⅱ)adsorbance of 483.9 mg g^(-1)along with good selectivity and recyclability.The adsorption is mainly chemisorption following the Langmuir mode.OACM-3 also shows high adsorbance for other heavy metal ions,e.g.256.6 mg g^(-1)for Pb(II),232.4 mg g^(-1)for Zn(II),and 198.7 mg g^(-1)for Cu(II).This work expands the mechnochemical reaction of CaC_(2)with carbonates and possibly other oxyanionic salts,provides a new synthesis approach for functional alkynyl carbon materials with excellent adsorption performance for heavy metal ions,as well as a feasible approach for CO2 resource utilization.

Active Machine Learning for Chemical Engineers:A Bright Future Lies Ahead!

By combining machine learning with the design of experiments,thereby achieving so-called active machine learning,more efficient and cheaper research can be conducted.Machine learning algorithms are more flexible and are better than traditional design of experiment algorithms at investigating processes spanning all length scales of chemical engineering.While active machine learning algorithms are maturing,their applications are falling behind.In this article,three types of challenges presented by active machine learning—namely,convincing the experimental researcher,the flexibility of data creation,and the robustness of active machine learning algorithms—are identified,and ways to overcome them are discussed.A bright future lies ahead for active machine learning in chemical engineering,thanks to increasing automation and more efficient algorithms that can drive novel discoveries.

Multiple chemical warfare agent simulant decontamination by self-driven microplasma

Low-temperature plasma is a green and high-efficiency technology for chemical warfare agent(CWA)decontamination.However,traditional plasma devices suffer from the problems of highpower composition and large power-supply size,which limit their practical applications.In this paper,a self-driven microplasma decontamination system,induced by a dielectric-dielectric rotary triboelectric nanogenerator(dd-r TENG),was innovatively proposed for the decontamination of CWA simulants.The microplasma was characterized via electrical measurements,optical emission spectra and ozone concentration detection.With an output voltage of-3460 V,the dd-r TENG can successfully excite microplasma in air.Reactive species,such as OH,O(1D),Hαand O3were detected.With input average power of 0.116 W,the decontamination rate of 2-chloroethyl ethyl sulfide reached 100%within 3 min of plasma treatment,while the decontamination rates of malathion and dimethyl methylphosphonate reached(65.92±1.65)%and(60.88±1.92)%after 7 min of plasma treatment,respectively.In addition,the decontamination rates gradually decreased with the increase in the simulant concentrations.Typical products were identified and analyzed.This study demonstrates the broad spectrum and feasibility of the dd-r TENG-microplasma for CWA elimination,which provides significant guidance for their practical applications in the future.

Chemical looping oxidative propane dehydrogenation controlled by oxygen bulk diffusion over FeVO_(4)oxygen carrier pellets

The oxygen distribution and evolution within the oxygen carrier exert significant influence on chemical looping processes.This paper describes the influence of oxygen bulk diffusion within FeVO4 oxygen carrier pellets on the chemical looping oxidative propane dehydrogenation(CL-ODH).During CL-ODH,the oxygen concentration at the pellet surface initially decreased and then maintained stable before the final decrease.At the stage with the stable surface oxygen concentration,the reaction showed a stable C3H6 formation rate and high C3H6 selectivity.Therefore,based on Fick’s second law,the oxygen distribution and evolution in the oxygen carrier at this stage were further analyzed.It was found that main reactions of selective oxidation and over-oxidation were controlled by the oxygen bulk diffusion.C3H8 conversion rate kept decreasing during this stage due to the decrease of the oxygen flux caused by the decline of oxygen gradient within the oxygen carrier,while C3H6 selectivity increased due to the decrease of overoxidation.In addition,reaction rates could increase with the propane partial pressure due to the increase of the oxygen gradient within the oxygen carrier until the bulk transfer reached its limit at higher propane partial pressure.This study provides fundamental insights for the diffusion-controlled chemical looping reactions.

High throughput screening of single atomic catalysts with optimized local structures for the electrochemical oxygen reduction by machine learning

Single atomic catalysts(SACs),especially metal-nitrogen doped carbon(M-NC)catalysts,have been extensively explored for the electrochemical oxygen reduction reaction(ORR),owing to their high activity and atomic utilization efficiency.However,there is still a lack of systematic screening and optimization of local structures surrounding active centers of SACs for ORR as the local coordination has an essential impact on their electronic structures and catalytic performance.Herein,we systematic study the ORR catalytic performance of M-NC SACs with different central metals and environmental atoms in the first and second coordination sphere by using density functional theory(DFT)calculation and machine learning(ML).The geometric and electronic informed overpotential model(GEIOM)based on random forest algorithm showed the highest accuracy,and its R^(2) and root mean square errors(RMSE)were 0.96 and 0.21,respectively.30 potential high-performance catalysts were screened out by GEIOM,and the RMSE of the predicted result was only 0.12 V.This work not only helps us fast screen high-performance catalysts,but also provides a low-cost way to improve the accuracy of ML models.

Cu(OH)_(2)/CMC one-dimensional composite-nanofiber-based electrochemical sensor for aspirin detection

Copper-based nanomaterials have been widely used in catalysis,electrodes,and other applications due to their unique electron-transfer properties.In this work,an efficient electrochemical sensor based on an electrode modified with one-dimensional Cu(OH)_(2)/carboxymethyl cellulose(CMC)composite nanofibers was fabricated and investigated for the detection of aspirin.Scanning electron microscopy was employed to examine the morphological characteristics of these composite nanofibers.Cyclic voltammetry and electrochemical impedance spectroscopy were used to assess the electrochemical performance of a Cu(OH)_(2)/CMC composite nanofiber-modified electrode.The findings indicate that the modified electrode has a very high sensitivity to aspirin.The observed enhanced performance could be a result of the high surface-to-volume ratio of the composite nanofibers and their superior electron-transport characteristics,which may hasten electron transfer between aspirin and the surfaces of the modified electrode.This detection technique also demonstrated strong selectivity for aspirin.These findings imply that the technique can be applied as a highly effective and selective approach to aspirin measurement in biological science.

Extend ethylene aromatization single-event kinetic modeling with physical and chemical descriptor based on ZSM-5 catalyst

The ethylene aromatization is critical for the methanol to aromatics and light alkane dehydroaromatization process.The single-event microkinetic(SEMK)model combining the linear free energy theory and solid acid distribution concept were established and extend for the ethylene aromatization process,which can reduce the kinetic parameters and simplify the reaction network by comparison with the SEMK model including subtype elementary steps based on the type of carbenium ions.Further introducing deactivation parametersφinto the model and applying the linear free energy model to the deactivation experimental data,the obtained deactivation parametersφindicate that the carbon deposition precursors have the greatest impact on reducing the reaction rate of single-molecular reactions and the smallest impact on the hydrogen transfer reaction.Meanwhile,according to the change of reaction enthalpy,effect of carbenium ion structure on methylation,ethylation,cyclization and endo-βscission was investigated by introducing linear free energy concept into the SEMK model.The effect of different acid strengths on elementary steps was investigated based on the acid strength distribution model,it was found that the methylation and oligomerization reactions,the ali-βscission reaction,endo-βscission reaction and the cyclization reaction were more sensitive to strong acidity sites.The physisorption and chemisorption heat are separated from the protonation heat in the linear free energy kinetic model and the acid strength distribution kinetic model,and the absolute values of the obtained physisorption and chemisorption heat increase with the carbon number of carbenium ions.Furthermore,the parameters of the acid strength distribution kinetic model were applied to propane dehydroaromatization on H-ZSM-5 and the ethane dehydroaromatization on Zn/ZSM-5 to confirm the independence of parameters in the SEMK model with the similar reaction network.

A novel calculation strategy for optimized prediction of the reduction of electrochemical window at anode

The reduction of the electrochemical window(EW)of electrolytes plays a significant role in assessing their compatibility with the anode in lithium-ion batteries.However,the accurate calculation of the reduction of EW is still challenging due to missing the solvation effects,condensation effects,kinetic factors,and the passivation on anodes.The theoretical prediction of the intrinsic and apparent EW is confirmed by a comprehensive experimental analysis of ethylene carbonatedimethyl carbonate(EC-DMC)electrolytes,combining linear sweep voltammetry(LSV)and gas chromatography-mass spectrometry(GC-MS).The proposed novel kinetic normal distribution theory model can quantitatively explain the current density from LSV and affirm acetaldehyde(MeCHO)as one of the primary reduction products of EC.The solvent effect restricts the intrinsic EW of EC-DMC without lithium salt to 2.6 V(vs.Li^(+)/Li)arising from the Marcus-Gerischer theory and the passivation of MeCHO on the anode broadens the apparent EW to 0.3 V(vs.Li^(+)/Li)arising from the normal distribution of the lowest unoccupied molecular orbital(LUMO)for MeCHO produced by thermal motion.In addition,the passivation on the anode depends intensively on the lithium salt,resulting in more complicated influences on the apparent EW.

Sputtered Stainless Steel on Silicon Photoanode for Stable Seawater Splitting in Photoelectrochemical Flow Cell

Photoelectrochemical(PEC)seawater splitting is a promising method for the direct utilization of solar energy and abundant seawater resources for hydrogen production.Photoelectrodes are susceptible to various ions in seawater and complicated competitive reactions,resulting in the failure of photoelectrodes.This paper proposes the design and fabrication of diff erent sputtered stainless steel(SS)fi lms deposited on silicon photoanodes,completely isolating the electrolytes and semiconductor substrate.Upon coupling with the PEC flow cell,the back-illuminated photoanode coated with 316 SS cocatalyst achieves stable operation for 70 h in natural seawater with a highly alkaline KOH(30 wt.%,7.64 mol/L)electrolyte due to the remarkable protection eff ect of the substrate from stainless steel,while the PEC seawater splitting system achieves a record hydrogen production rate of 600μmol/(h·cm^(2)).An appropriate Ni/Fe ratio in the SS ensures remarkable oxygen evolution activity,while chromic oxide ensures the effective anticorrosion effect by adjusting the microenvironment of the photoanodes.Moreover,fabricating PEC flow cells with photoanodes coated with SS cocatalysts are a viable strategy for PEC seawater splitting.

Laser-assisted synthesis of Au NPs on MgO/chitosan:Applications in electrochemical hydrogen storage

Hydrogen with high energy density is an environmental alternative to fossil fuels which can respond to the demand for energy considering environmental conditions.It can be stored on porous materials employing physical interaction(e.g.adsorption process).The H2storage capacity of materials can be evaluated through electrochemical methods.Therefore,a fast and straightforward approach was employed to fabricate magnesium oxide/chitosan/Au nanoparticles(Mg O/CS/Au)nanocomposites with porous structure for electrochemical hydrogen storage.Herein,laser ablation in water as a fast and green method was utilized to obtain Au nanoparticles(Au NPs).The obtained Au NPs were loaded on Mg O/CS nanocomposite through physical mixing.Structural and morphological investigation of nanocomposites display spherically shaped Au NPs with a diameter of 49–58 nm agglomerated on the Mg O/CS.Drop casting,the fast and cost-effective method was deployed to deposit the benign,and reusable Mg O/CS/Au-x(x is Au NPs weight percentage of 1,3 and 5 wt.%)nanocomposites on stainless steel mesh and their electrochemical hydrogen storage were measured by cyclic voltammetry(CV),indicating good stability and significant hydrogen storage capacity(28 C/g)after 300 CV scans for MgO/CS/Au-1 sample.

Recent update on electrochemical CO_(2)reduction catalyzed by metal sulfide materials

Seeking and developing efficient CO_(2)reduction reaction(CO_(2)RR)electrocatalysts is a hot topic in this era of global warming.Among material candidates for sustainable and cost-effective applications,metal sulfides have attracted attention as promising nature-inspired materials due to multiple adsorption sites which are enhanced by the covalent character of sulfur.This article summarizes the current status regarding the utilization and development of metal sulfide materials as CO_(2)RR electrocatalysts.First,the research background and basic principles of electrochemical CO_(2)RR are introduced.Next,an overview of the main obstacles to developing efficient CO_(2)RR electrocatalysts is presented.The section is followed by a summary of the empirical evidence supporting the application of metal sulfides as CO_(2)RR electrocatalysts beside nature-inspired motivation.The summary of synthesis methods of various metal sulfides is also presented.Furthermore,the paper also highlights the recent works on metal sulfide as efficient CO_(2)RR including the undertaking strategy on the activity enhancement,and finally,discusses the challenges and prospect of metal sulfides-based CO_(2)RR electrocatalysts.Despite recent efforts,metal sulfides remain relatively unexplored as materials for CO_(2)RR electrocatalytic applications.Therefore,this review aims to stimulate novel ideas and research for improved catalyst designs and functionality.

Enabling heterogeneous catalysis to achieve carbon neutrality: Directional catalytic conversion of CO_(2) into carboxylic acids

The increase in anthropogenic carbon dioxide(CO_(2))emissions has exacerbated the deterioration of the global environment,which should be controlled to achieve carbon neutrality.Central to the core goal of achieving carbon neutrality is the utilization of CO_(2) under economic and sustainable conditions.Recently,the strong need for carbon neutrality has led to a proliferation of studies on the direct conversion of CO_(2) into carboxylic acids,which can effectively alleviate CO_(2) emissions and create high-value chemicals.The purpose of this review is to present the application prospects of carboxylic acids and the basic principles of CO_(2) conversion into carboxylic acids through photo-,electric-,and thermal catalysis.Special attention is focused on the regulation strategy of the activity of abundant catalysts at the molecular level,inspiring the preparation of high-performance catalysts.In addition,theoretical calculations,advanced technologies,and numerous typical examples are introduced to elaborate on the corresponding process and influencing factors of catalytic activity.Finally,challenges and prospects are provided for the future development of this field.It is hoped that this review will contribute to a deeper understanding of the conversion of CO_(2) into carboxylic acids and inspire more innovative breakthroughs.

Intelligent Small Sample Defect Detection of Concrete Surface Using Novel Deep Learning Integrating Improved YOLOv5

Dear Editor,This letter presents an intelligent small sample defect detection of concrete surface using novel deep learning integrating the improved YOLOv5 based on the Wasserstein GAN(WGAN)enhancement algorithm.The proposed method is capable of producing top-notch data sets to address the issues of insufficient samples and substandard quality.

d-Orbital steered FeN_(4)moiety through N,S dual-site adjustation for zinc-air flow battery

The implementation of pristine covalent organic polymer(CO_(2)P)with well-defined structure as air electrode may spark fresh vitality to rechargeable zinc-air flow batteries(ZAFBs),but it still remains challenges in synergistically regulating their electronic states and structural porosity for the great device performance.Here,we conquer these issues by exploiting N and S co-doped graphene with COP rich in metal-ligand nitrogen to synergistically construct an effective catalyst for oxygen reduction reaction(ORR).Among them,the N and S co-doped sites with high electronegativity properties alter the number of electron occupations in the d orbital of the iron centre and form electron-transfer bridges,thereby boosting the selectivity of the ORR-catalysed four-electron pathway.Meanwhile,the introduction of COP materials aids the formation of pore interstices in the graphene lamellae,which both adequately expose the active sites and facilitate the transport of reactive substances.Benefiting from the synergistic effect,as-prepared catalyst exhibits excellent half-wave potentials(E_(1/2)=912 mV)and stability(merely 8.8%drop after a long-term durability test of 50000 s).Further,ZAFBs assembled with the N/SG@CO_(2)P catalyst demonstrate exceptional power density(163.8 mW cm^(-2))and continuous charge and discharge for approximately 140 h at 10 mA cm^(-2),outperforming the noble-metal benchmarks.

THE NONLINEAR STABILITY OF PLANE PARALLEL SHEAR FLOWS WITH RESPECT TO TILTED PERTURBATIONS

The nonlinear stability of plane parallel shear flows with respect to tilted perturbations is studied by energy methods.Tilted perturbation refers to the fact that perturbations form an angleθ∈(0,π/2)with the direction of the basic flows.By defining an energy functional,it is proven that plane parallel shear flows are unconditionally nonlinearly exponentially stable for tilted streamwise perturbation when the Reynolds number is below a certain critical value and the boundary conditions are either rigid or stress-free.In the case of stress-free boundaries,by taking advantage of the poloidal-toroidal decomposition of a solenoidal field to define energy functionals,it can be even shown that plane parallel shear flows are unconditionally nonlinearly exponentially stable for all Reynolds numbers,where the tilted perturbation can be either spanwise or streamwise.