Recent progress and challenges in structural construction strategy of metal-based catalysts for nitrate electroreduction to ammonia

Ammonia plays an essential role in human production and life as a raw material for chemical fertilizers.The nitrate electroreduction to ammonia reaction(NO_(3)RR)has garnered attention due to its advantages over the Haber-Bosch process and electrochemical nitrogen reduction reaction.Therefore,it represents a promising approach to safeguard the ecological environment by enabling the cycling of nitrogen species.This review begins by discussing the theoretical insights of the NO_(3)RR.It then summarizes recent advances in catalyst design and construction strategies,including alloying,structure engineering,surface engineering,and heterostructure engineering.Finally,the challenges and prospects in this field are presented.This review aims to guide for enhancing the efficiency of electrocatalysts in the NO_(3)RR,and offers insights for converting NO_(3)-to NH_(3).

Response of Rice Growth and Nutrient Absorption in a SalineAlkali Paddy to Different Nitrogen Fertilizer Applications

Nitrogen(N),phosphorus(P)and carbon(C)are essential nutrients for rice growth and development,but the response of nutrient absorption by rice plants to different types of nitrogen fertilizer(N-fertilizer)under saline-alkali conditions is unclear.This study conducted a 147-day field-scale experiment to evaluate rice biomass and nutrient absorption capacity with five N-fertilizer applications.The results showed that the biomass.

The Decarbonization of Construction—How Can Alkali-Activated Materials Contribute?

1.Introduction and context Enormous emphasis is currently being paid to the decarbonization of the global built environment as a leading priority for the engineering community and related industrial sectors[1].One of the main contributors to the overall emissions footprint of the built environment-and thus a cornerstone of efforts to achieve decarbonization-is the emissions profile of construction materials during their production and utilization.The cement and concrete sector is the largest-volume contributor to the emissions incurred in meeting the world’s construction material needs and is therefore targeted in the discussion of the deep,rapid decarbonization that must be achieved in order to minimize irreversible damage to the Earth and its ecosystems.

Alkali Tolerance of Concrete Internal Curing Agent Based on Sodium Carboxymethyl Starch

Internal curing agents (ICA) based on super absorbent polymer have poor alkali tolerance and reduce the early strength of concrete.An alkali tolerate internal curing agent (CAA-ICA) was designed and prepared by using sodium carboxymethyl starch (CMS) with high hydrophilicity,acrylic acid (AA) containing anionic carboxylic group and acrylamide (AM) containing non-ionic amide group as the main raw materials.The results show that the ratio of CAA-ICA alkali absorption solution is higher than that existing ICA,which solves the low water absorption ratio of the ICA in alkali environment.The water absorption ratio of CAA-ICA in saturated Ca(OH)_(2) solution is 95.8 g·g^(-1),and the alkali tolerance coefficient is 3.4.The application of CAA-ICA in cement-based materials can increase the internal relative humidity and miniaturize the pore structure.The compressive strength of mortar increases up to 12.95%at 28 d,which provids a solution to overcome the reduction of the early strength.

Residual alkali-evoked cross-linked polymer layer for anti-air-sensitivity LiNi_(0.89)Co_(0.06)Mn_(0.05)O_(2)cathode

High-energy density lithium-ion batteries(LIBs)with layered high-nickel oxide cathodes(LiNi_(x)Co_(y)Mn_(1-x-y)O_(2),x≥0.8)show great promise in consumer electronics and vehicular applications.However,LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)faces challenges related to capacity decay caused by residual alkalis owing to high sensitivity to air.To address this issue,we propose a hazardous substances upcycling method that fundamentally mitigates alkali content and concurrently induces the emergence of an anti-air-sensitive layer on the cathode surface.Through the neutralization of polyacrylic acid(PAA)with residual alkalis and then coupling it with 3-aminopropyl triethoxysilane(KH550),a stable and ion-conductive cross-linked polymer layer is in situ integrated into the LiNi_(0.89)Co_(0.06)Mn_(0.05)O_(2)(NCM)cathode.Our characterization and measurements demonstrate its effectiveness.The NCM material exhibits impressive cycling performance,retaining 88.4%of its capacity after 200 cycles at 5 C and achieving an extraordinary specific capacity of 170.0 mA h g^(-1) at 10 C.Importantly,this layer on the NCM efficiently suppresses unfavorable phase transitions,severe electrolyte degradation,and CO_(2)gas evolution,while maintaining commendable resistance to air exposure.This surface modification strategy shows widespread potential for creating air-stable LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)cathodes,thereby advancing high-performance LIBs.

Fundamental Study on Alkali-Activated Slag System with Sodium Carbonate or Calcium Hydroxide

Cement as a building material, has high fluidity, compressive strength, and durability, but carbon dioxide emissions during cement production are a major problem. As one of the countermeasures, alkali-activated cement using blast furnace slag powder with alkaline stimulants is considered to be a very promising solution for reducing carbon dioxide emissions, but there is a lack of information about the fundamental properties of alkali-activated materials. This study presents an experimental investigation of the fundamental properties of an alkali-activated slag system with sodium carbonate (NC) and calcium hydroxide (CH). The effects of calcium sulfo-aluminate (CSA) and shrinkage reducing agent (SRA) on the properties of blast furnace slag (BFS) based alkali-activated mixture were also investigated. In the experiments, fundamental characteristics including compressive strength, drying shrinkage, and water penetration tests of mortar were evaluated. Porosity, pH, and ignition loss were measured to verify the effectiveness of the materials. The experimental investigation revealed that the compressive strength was increased with the increasing replacement rates of NC in the BFS mortar, and in the case of water to BFS ratio of 0.45 with sodium carbonation addition contents 10 wt.%, the compressive strength for 28 days of curing reaches more than 50 MPa. Low water to BFS ratio and higher addition ratio of NC had a positive effect on the compressive strength development of mortar. Incorporating NC into BFS would affect the decrease in porosity and increase in ignition loss, leading to higher compressive strength. There was a negligible change to the compressive strength, porosity, pH, and ignition loss of BFS samples made with CH, thus, the addition rates of CH to BFS have no or little significant effect on the fundamental properties of alkali-activated cement. From the results of drying shrinkage and water penetration tests, the addition of NC and CH only to BFS exhibited poor drying shrinkage and water penetration characteristics. However, these problems may be overcome due to the use of CSA or SRA in the alkali-activated system made with NC or CH.

Electrodeposition:Synthesis of advanced transition metal-based catalyst for hydrogen production via electrolysis of water

Developing lower-cost and higher-effective catalyst to support hydrogen(H_(2))production by electrochemical water-splitting has been recognized as a preferred strategy to drive the clean energy utilization.As a credible technology for the synthesis of functional materials,electrodeposition has attracted widespread attention,especially suitable for non-noble transition metal-based catalysts(TMCs).Recently,lots of researchers have been devoted to this hot research direction with plentiful achievements,however,a comprehensive review towards this area is still missing.Hence,we summarize the past research progress,presents the technical characteristics of electrodeposition from the viewpoint of fundamental theory and influence factors for the electrochemical deposition behavior,and introduce its application in various of TMCs with versatile nanostructures and compositions.Except a deeper and more comprehensive cognition of electrodeposition,we further discuss the catalyst’s optimized hydrogen evolution reaction(HER),oxygen evolution reaction(OER)performance as well as overall water splitting that combined with the synthetic process.Finally,we conclude the technical advantages towards electrodeposition,propose challenge and future research directions in this promising field.This timely review aims to promote a deeper understanding of effective catalysts obtained via electrodeposition strategy,and provide new guidance for the design and synthesis of future catalysts for hydrogen production.

Development of Metal and Metal-Based Composites Anode Materials for Potassium-Ion Batteries

Potassium-ion batteries(KIBs)are considered the next powerful potential generation energy storage system because of substantial potassium resource availability and similar characteristics with lithium.Unfortunately,the actual application of KIBs is inferior to that of lithium-ion batteries(LIBs),in which the fi nite energy density,ordinary circular life,and underdeveloped fabrication technique dominate the key constraints.Various works have recently been directed to growing novel anode electrodes with superior electrochemical capability.Noticeably,metals/metal oxides materials(e.g.,Sb,Sn,Zn,SnO_(2),and MoO_(2))have been widely investigated as KIBs anodes because of high theoretical capacity,suggesting outstanding promise for high-energy KIBs.In this review,the latest research of metals/metal oxides electrodes for potassium storage is summarized.The major strategies to control the electrochemical property of metals/metal oxides electrodes are discussed.Finally,the future investigation foreground for these anode electrodes has been proposed.

Hydrogen Production via Hydrolysis and Alcoholysis of Light Metal-Based Materials:A Review

As an environmentally friendly and high-density energy carrier,hydrogen has been recognized as one of the ideal alternatives for fossil fuels.One of the major challenges faced by“hydrogen economy”is the development of efficient,low-cost,safe and selective hydrogen generation from chemical storage materials.In this review,we summarize the recent advances in hydrogen production via hydrolysis and alcoholysis of light-metal-based materials,such as borohydrides,Mg-based and Al-based materials,and the highly efficient regeneration of borohydrides.Unfortunately,most of these hydrolysable materials are still plagued by sluggish kinetics and low hydrogen yield.While a number of strategies including catalysis,alloying,solution modification,and ball milling have been developed to overcome these drawbacks,the high costs required for the“one-pass”utilization of hydrolysis/alcoholysis systems have ultimately made these techniques almost impossible for practical large-scale applications.Therefore,it is imperative to develop low-cost material systems based on abundant resources and effective recycling technologies of spent fuels for efficient transport,production and storage of hydrogen in a fuel cell-based hydrogen economy.

Effects of Heavy Metal Pollution of Apple Orchard Surface Soils Associated with Past Use of Metal-Based Pesticides on Soil Microbial Biomass and Microbial Communities

Apple orchard surface soils in Japan are polluted with copper (Cu), lead (Pb), and arsenic (As) due to long-term use of metal-based pesticides. We investigated the effects of heavy metals accumulated in the surface soils in apple orchards on the microbial biomass and the microbial communities. Soil samples were taken from a chestnut orchard (unpolluted control) and five apple orchards with different degrees of heavy metal pollution. Total concentrations of Cu, Pb, and As in soil ranged from 29 to 931 mg/kg, 35 to 771 mg/kg, and 11 to 198 mg/kg, respectively. The amount of microbial biomass carbon expressed on a soil organic carbon basis decreased with increasing concentrations of heavy metals. Thus, the heavy metals that accumulated in apple orchard surface soils had adverse effects on the soil microbial biomass. The analysis of phospholipid fatty acid (PLFA) composition indicated that the microbial community structure had changed because of the pesticide-derived heavy metals in soil. The relative abundance of gram-positive bacterial marker PLFAs increased and that of fungal marker PLFA decreased with increasing concentrations of heavy metals in soil. Denaturing gradient gel electrophoreses targeting the 16S ribosomal RNA gene of bacteria and the 18S ribosomal RNA gene of fungi also showed shifts in the composition of bacterial and fungal communities induced by soil pollution with heavy metals. However, the diversity of microbial communities was not significantly affected by the heavy metal pollution. This was attributable to the adaptation of the microbial communities in apple orchard surface soils to heavy metals derived from previously used pesticides.

Effects of biochar-amended alkali-activated slag on the stabilization of coral sand in coastal areas

Coral sand is widely encountered in coastal areas of tropical and subtropical regions.Compared with silica sand,it usually exhibits weaker performance from the perspective of engineering geology.To improve the geomechanical performance of coral sand and meet the requirement of foundation construction in coastal areas,a novel alkali activation-based sustainable binder was developed.The alkaliactivated slag(AAS)binder material was composed of ground granulated blast-furnace slag(GGBS)and hydrated lime with the amendment of biochar,an agricultural waste-derived material.The biocharamended AAS stabilized coral sand was subjected to a series of laboratory tests to determine its mechanical,physicochemical,and microstructural characteristics.Results show that adding a moderate amount of biochar in AAS could improve soil strength,elastic modulus,and water holding capacity by up to 20%,70%,and 30%,respectively.Moreover,the addition of biochar in AAS had a marginal effect on the sulfate resistance of the stabilized sand,especially at high biochar content.However,the resistance of the AAS stabilized sand to wet-dry cycles slightly deteriorated with the addition of biochar.Based on these observations,a conceptual model showing biochar-AAS-sand interactions was proposed,in which biochar served as an internal curing agent,micro-reinforcer,and mechanically weak point.

Understanding the growth mechanisms of metal-based core–shell nanostructures revealed by in situ liquid cell transmission electron microscopy

Metal-based core-shell nanostructures have garnered enduring interest due to their unique properties and functionalities.However,their growth and transformation mechanisms in liquid media remain largely unknown because they lack direct observation of the dynamic growth process with high spatial and temporal resolution.Developing the in situ liquid cell transmission electron microscopy(TEM)technique offers unprecedented real-time imaging and spectroscopy capabilities to directly track the evolution of structural and chemical transformation of metal-based core–shell nanostructures in liquid media under their working condition.Here,this review highlights recent progress in utilizing in situ liquid cell TEM characterization technique in investigating the dynamic evolution of material structure and morphology of metal-based core–shell nanostructures at the nano/atomic scale in real-time.A brief introduction of the development of liquid cells for in situ TEM is first given.Subsequently,recent advances in in situ liquid cell TEM for the fundamental study of growth mechanisms of metal based core–shell nanostructures are discussed.Finally,the challenge and future developments of metalbased core–shell nanostructures for in situ liquid cell TEM are proposed.Our review is anticipated to inspire ongoing interest in revealing unseen growth dynamics of core–shell nanostructures by in situ liquid cell TEM technique.

Orientational Separation of Sulfur in Petroleum Coke by Alkali Calcining and Reflux Washing

The application of high-sulfur petroleum coke after desulfurization in aluminum electrolysis anodes is an important development trend. However, removing sulfur from high-sulfur petroleum coke is still a significant challenge.This study proposes alkali calcining and reflux washing to examine the impacts of temperature, particle size, the mass ratio of Na_(2)CO_(3) to NaOH, and total sodium addition on the desulfurization efficiency and mechanism. The results show that the desulfurization rate increases with increasing temperature, increasing total sodium content, and decreasing particle size. The addition of alkali can significantly reduce the opening-ring reaction temperature of thiophene and convert organic sulfur into inorganic sulfur(Na_(2)S). Three washing methods were compared, and reflux washing was selected to separate inorganic sulfur(Na_(2)S) from calcined petroleum coke. The sulfur content in petroleum coke decreased from 7.29% to 1.90%, with a desulfurization rate of 80.13% under optimal conditions. The petroleum coke was analyzed before and after desulfurization using X-Ray diffraction(XRD), Scanning Electron Microscopy(SEM), Infrared Spectroscopy(IR), Thermogravimetric Analysis and Differential Scanning Calorimetry(TG-DSC), Gaschromatography-mass Spectrometry(GC-MS). The results show that thiophene and benzothiophene in petroleum coke are decomposed and converted into octane and ethyl cyclohexane. These new observations are expected to provide further understanding and guidance for the utilization of highsulfur petroleum coke.

Genome-wide analysis of soybean DnaJA-family genes and functional characterization of GmDnaJA6 responses to saline and alkaline stress

Plant Dna JA proteins act as molecular chaperones in response to environmental stressors.The purpose of this study was to characterize the function and regulatory mechanisms of Dna JA genes in soybean.Gene expression profiles in various soybean tissues at various stages of development indicated that Gm Dna JAs function in the coordination of stress and plant hormone responses.Gm Dna JA6 was identified as a candidate regulator of saline and alkaline stress resistance and Gm Dna JA6 overexpression lines showed increased soybean saline and alkaline tolerance.Dna J interacted with Hsp70,and Gm Hsp70 increased the saline and alkaline tolerance of plants with chimeric soybean hairy roots.

Emerging Carbon Nanotube-Based Nanomaterials for Stable and Dendrite-Free Alkali Metal Anodes:Challenges,Strategies,and Perspectives

Alkali metals(Li,Na,and K)are promising candidates for high-performance rechargeable alkali metal battery anodes due to their high theoretical specific capacity and low electrochemical potential.However,the actual application of alkali metal anodes is impeded by the challenges of alkali metals,including their high chemical reactivity,uncontrolled dendrite growth,unstable solid electrolyte interphase,and infinite volume expansion during cycling processes.Introducing carbon nanotube-based nanomaterials in alkali metal anodesis an effective solution to these issues.These nanomaterials have attracted widespread attention owing to their unique properties,such as their high specific surface area,superior electronic conductivity,and excellent mechanical stability.Considering the rapidly growing research enthusiasm for this topic in the last several years,we review recent progress on the application of carbon nanotube-based nanomaterials in stable and dendrite-free alkali metal anodes.The merits and issues of alkali metal anodes,as well as their stabilizing strategies are summarized.Furthermore,the relationships among methods of synthesis,nano-or microstructures,and electrochemical properties of carbon nanotube-based alkali metal anodes are systematically discussed.In addition,advanced characterization technologies on the reaction mechanism of carbon nanotube-based nanomaterials in alkali metal anodes are also reviewed.Finally,the challenges and prospects for future study and applications of carbon nanotube-based AMAs in high-performance alkali metal batteries are discussed.

Theoretical study on the morphology of cobalt nanoparticles modulated by alkali metal promoters

Cobalt nanoparticles(NPs)catalysts are extensively used in heterogeneous catalytic reactions,and the addition of alkali metal promoters is a common method to modulate the catalytic performance because the catalyst's surface structures and morphologies are sensitive to the addition of promoters.However,the underlying modulation trend remains unclear.Herein,the adsorption of alkali metal promoters(Na and K)on the surfaces of face-centered-cubic(FCC)and hexagonal-closest packed(HCP)polymorphous cobalt was systematically investigated using density functional theory.Furthermore,the effect of alkali promoters on surface energies and nanoparticle morphologies was revealed on the basis of Wulff theory.For FCC-Co,the exposed area of the(111)facet in the nanoparticle increases with the adsorption coverage of alkali metal oxide.Meanwhile,the(311),(110),and(100)facets would disappear under the higher adsorption coverage of alkali metals.For HCPCo,the Wulff morphology is dominated by the(0001)and(1011)facets and is independent of the alkali metal adsorption coverage.This work provides insights into morphology modulation by alkali metal promoters for the rational design and synthesis of cobalt-based nanomaterials with desired facets and morphologies.

Quantitative Extraction of p-Coumaric Acid and Ferulic Acid in Different Gramineous Materials and Structural Changes of Residual Alkali Lignin

Ferulic acid(FA)and p-coumaric acid(pCA)in bagasse,wheat straw,corn straw,and corncob were extracted by alkaline hydrolysis and characterized by gas chromatography(GC)and gas chromatography-mass spectrometry(GC-MS).It was found that the FA and most of the pCA in gramineous biomass could be dissociated and released after being treated with 1 M NaOH at 100℃for 4 h.The yields of pCA/FA in bagasse,wheat straw,corn straw,and corncob determined by GC-FID are 39.8/11.5,13.7/11.0,28.0/11.0,and 35.1/14.5 mg/g,respectively.The raw materials and the treated solid residues were characterized by gel-state 2D Heteronuclear Single Quantum Coherence Nuclear Magnetic Resonance(2D HSQC NMR).It was found that only a small amount of lignin was detected in the residue after alkali treatment,indicating that the alkali treatment conditions can effectively cleave the FA and pCA.Additionally,the lignin in the alkali solution was recovered and characterized by 2D HSQC NMR.The FA was not able to be detected by NMR,whereas a small amount of pCA remained in the alkali lignin.This study reveals the structural change of residual lignins during the quantitative isolation of FA and pCA,which is essential for the selective isolation of pCA/FA and valorization of residual alkali lignin.

Alkali Vapor Corrosion of Different Refractories at High Temperatures

Commercial high purity corundum brick,corundum-mullite brick,mullite brick,calcium hexaaluminate brick and calcium hexaaluminate-corundum brick were studied to investigate their reaction state and alkali vapor corrosion mechanism at 1370 and 1500℃.The results show that:(1)served in hot alkali vapor,the high-purity corundum brick has no obvious slag layer but expands dramatically;(2)the corundum-mullite brick shows obvious reactive expansion at 1370℃and melting corrosion happens at 1500℃;(3)at 1370℃alkali vapor and mullite brick react and form a slag layer without volume effect;when the temperature increases to 1500℃,the reaction melting corrosion intensifies;(4)the calcium hexaaluminate brick and the calcium hexaaluminate-corundum brick form a thin slag layer in alkali vapor,and the sample surface absorbs Na+to form a dense layer with small volume effect.

Promotion effects of alkali metals on iron molybdate catalysts for CO_(2)catalytic hydrogenation

CO_(2)hydrogenation is an attractive way to store and utilize carbon dioxide generated by industrial processes,as well as to produce valuable chemicals from renewable and abundant resources.Iron catalysts are commonly used for the hydrogenation of carbon oxides to hydrocarbons.Iron-molybdenum catalysts have found numerous applications in catalysis,but have been never evaluated in the CO_(2)hydrogenation.In this work,the structural properties of iron-molybdenum catalysts without and with a promoting alkali metal(Li,Na,K,Rb,or Cs)were characterized using X-ray diffraction,hydrogen temperatureprogrammed reduction,CO_(2)temperature-programmed desorption,in-situ^(57)Fe Mossbauer spectroscopy and operando X-ray adsorption spectroscopy.Their catalytic performance was evaluated in the CO_(2)hydrogenation.During the reaction conditions,the catalysts undergo the formation of an iron(Ⅱ)molybdate structure,accompanied by a partial reduction of molybdenum and carbidization of iron.The rate of CO_(2)conversion and product selectivity strongly depend on the promoting alkali metals,and electronegativity was identified as an important factor affecting the catalytic performance.Higher CO_(2)conversion rates were observed with the promoters having higher electronegativity,while low electronegativity of alkali metals favors higher light olefin selectivity.

Designing Advanced Liquid Electrolytes for Alkali Metal Batteries:Principles,Progress,and Perspectives

The ever-growing pursuit of high energy density batteries has triggered extensive efforts toward developing alkali metal(Li,Na,and K)battery(AMB)technologies owing to high theoretical capacities and low redox potentials of metallic anodes.Typically,for new battery systems,the electrolyte design is critical for realizing the battery electrochemistry of AMBs.Conventional electrolytes in alkali ion batteries are generally unsuitable for sustaining the stability owing to the hyper-reactivity and dendritic growth of alkali metals.In this review,we begin with the fundamentals of AMB electrolytes.Recent advancements in concentrated and fluorinated electrolytes,as well as functional electrolyte additives for boosting the stability of Li metal batteries,are summarized and discussed with a special focus on structure-composition-performance relationships.We then delve into the electrolyte formulations for Na-and K metal batteries,including those in which Na/K do not adhere to the Li-inherited paradigms.Finally,the challenges and the future research needs in advanced electrolytes for AMB are highlighted.This comprehensive review sheds light on the principles for the rational design of promising electrolytes and offers new inspirations for developing stable AMBs with high performance.