Enhanced structural stability and durability in lithium-rich manganese-based oxide via surface double-coupling engineering

Lithium-rich manganese-based oxides(LRMOs) exhibit high theoretical energy densities, making them a prominent class of cathode materials for lithium-ion batteries. However, the performance of these layered cathodes often declines because of capacity fading during cycling. This decline is primarily attributed to anisotropic lattice strain and oxygen release from cathode surfaces. Given notable structural transformations, complex redox reactions, and detrimental interface side reactions in LRMOs, the development of a single modification approach that addresses bulk and surface issues is challenging. Therefore,this study introduces a surface double-coupling engineering strategy that mitigates bulk strain and reduces surface side reactions. The internal spinel-like phase coating layer, featuring threedimensional(3D) lithium-ion diffusion channels, effectively blocks oxygen release from the cathode surface and mitigates lattice strain. In addition, the external Li_(3)PO_(4) coating layer, noted for its superior corrosion resistance, enhances the interfacial lithium transport and inhibits the dissolution of surface transition metals. Notably, the spinel phase, as excellent interlayer, securely anchors Li_(3)PO_(4) to the bulk lattice and suppresses oxygen release from lattices. Consequently, these modifications considerably boost structural stability and durability, achieving an impressive capacity retention of 83.4% and a minimal voltage decay of 1.49 m V per cycle after 150 cycles at 1 C. These findings provide crucial mechanistic insights into the role of surface modifications and guide the development of high-capacity cathodes with enhanced cyclability.

Rational surface charge engineering of haloalkane dehalogenase for boosting the enzymatic performance in organic solvent solutions

Biocatalysis in organic solvents(OSs)has numerous important applications,but native enzymes in OSs often exhibit limited catalytic performance.Herein,we proposed a computation-aided surface charge engineering strategy to improve the catalytic performance of haloalkane dehalogenase DhaA in OSs based on the energetic analysis of substrate binding to the DhaA surface.Several variants with enhanced OS resistance were obtained by replacing negative charged residues on the surface with positive charged residue(Arg).Particularly,a four-substitution variant E16R/E93R/E121R/E257R exhibited the best catalytic performance(five-fold improvement in OS resistance and seven-fold half-life increase in 40%(vol)dimethylsulfoxide).As a result,the overall catalytic performance of the variant could be at least 26 times higher than the wild-type DhaA.Fluorescence spectroscopy and molecular dynamics simulation studies revealed that the residue substitution mainly enhanced OS resistance from four aspects:(a)improved the overall structural stability,(b)increased the hydrophobicity of the local microenvironment around the catalytic triad,(c)enriched the hydrophobic substrate around the enzyme molecule,and(d)lowered the contact frequency between OS molecules and the catalytic triad.Our findings validate that computationaided surface charge engineering is an effective and ingenious rational strategy for tailoring enzyme performance in OSs.

Surface engineering of P2-type cathode material targeting long-cycling and high-rate sodium-ion batteries

The widespread interest in layered P2-type Mn-based cathode materials for sodium-ion batteries(SIBs)stems from their cost-effectiveness and abundant resources.However,the inferior cycle stability and mediocre rate performance impede their further development in practical applications.Herein,we devised a wet chemical precipitation method to deposit an amorphous aluminum phosphate(AlPO_(4),denoted as AP)protective layer onto the surface of P2-type Na_(0.55)Ni_(0.1)Co_(0.7)Mn_(0.8)O_(2)(NCM@AP).The resulting NCM@5AP electrode,with a 5 wt%coating,exhibits extended cycle life(capacity retention of78.4%after 200 cycles at 100 mA g^(-1))and superior rate performance(98 mA h g^(-1)at 500 mA g^(-1))compared to pristine NCM.Moreover,our investigation provides comprehensive insights into the phase stability and active Na^(+)ion kinetics in the NCM@5AP composite electrode,shedding light on the underlying mechanisms responsible for the enhanced performance observed in the coated electrode.

Electrochemical Carbon Dioxide Reduction to Ethylene:From Mechanistic Understanding to Catalyst Surface Engineering

Electrochemical carbon dioxide reduction reaction(CO_(2)RR)provides a promising way to convert CO_(2)to chemicals.The multicarbon(C_(2+))products,especially ethylene,are of great interest due to their versatile industrial applications.However,selectively reducing CO_(2)to ethylene is still challenging as the additional energy required for the C–C coupling step results in large overpotential and many competing products.Nonetheless,mechanistic understanding of the key steps and preferred reaction pathways/conditions,as well as rational design of novel catalysts for ethylene production have been regarded as promising approaches to achieving the highly efficient and selective CO_(2)RR.In this review,we first illustrate the key steps for CO_(2)RR to ethylene(e.g.,CO_(2)adsorption/activation,formation of~*CO intermediate,C–C coupling step),offering mechanistic understanding of CO_(2)RR conversion to ethylene.Then the alternative reaction pathways and conditions for the formation of ethylene and competitive products(C_1 and other C_(2+)products)are investigated,guiding the further design and development of preferred conditions for ethylene generation.Engineering strategies of Cu-based catalysts for CO_(2)RR-ethylene are further summarized,and the correlations of reaction mechanism/pathways,engineering strategies and selectivity are elaborated.Finally,major challenges and perspectives in the research area of CO_(2)RR are proposed for future development and practical applications.

Selective sulfur conversion with surface engineering of electrocatalysts in a lithium-sulfur battery

The sluggish kinetics of multiphase sulfur conversion with homogeneous and heterogeneous electrochemical processes,causing the“shuttle effect”of soluble polysulfide species(PSs),is the challenges in terms of lithium-sulfur batteries(LSBs).In this paper,a Mn_(3)O_(4-x) catalyst,which has much higher activity for heterogeneous reactions than for homogeneous reactions(namely,preferentialactivity catalysts),is designed by surface engineering with rational oxygen vacancies.Due to the rational design of the electronic structure,the Mn_(3)O_(4-x) catalyst prefers to accelerate the conversion of Li2S4 into Li_(2)S_(2)/Li_(2)S and optimize Li_(2)S deposition,reducing the accumulation of PSs and thus suppressing the“shuttle effect.”Both density functional theory calculations and in situ X-ray diffraction measurements are used to probe the catalytic mechanism and identify the reaction intermediates of MnS and Li_(y)Mn_(z)O_(4-x) for fundamental understanding.The cell with Mn_(3)O_(4-x) delivers an ultralow attenuation rate of 0.028% per cycle over 2000 cycles at 2.5 C.Even with sulfur loadings of 4.93 and 7.10mg cm^(-2) in a lean electrolyte(8.4μL mg s^(-1)),the cell still shows an initial areal capacity of 7.3mAh cm^(-2).This study may provide a new way to develop preferential-activity heterogeneous-reaction catalysts to suppress the“shuttle effect”of the soluble PSs generated during the redox process of LSBs.

Boosting the Performance Gain of Ru/C for Hydrogen Evolution Reaction Via Surface Engineering

The surface properties of catalysts determine the intrinsic activity and adaptability.Ruthenium is regarded as a potential candidate to substitute platinum for water electrolysis due to the low cost and analogous electronic structures while it suffers from severe dissolution and stability problems.Herein,the modification of Ru/C with atomically dispersed cobalt atoms is achieved via a simple thermal doping method.The newly formed amorphous shell with Ru-Co sites on the Ru/C catalyst improved the hydrogen evolution reaction activity and stability significantly.Impressively,the obtained Co1Ru@Ru/CN_(x)catalyst exhibited an overpotential as low as 30 mV at 10 mA cm^(-2)in an alkaline medium,which is among the best HER catalysts reported so far.The oxygen oxophile Co prevents the fast oxidation and dissolution of Ru species,ensuring outstanding long-term durability up to 70 h.Theoretical calculations reveal that the Ru-Co coordination acts as a more active site for water dissociation than the Ru-Ru.Meanwhile,the"Ru-Co shell/Ru core"structures show high adaptability for the reaction conditions.This simple doping strategy offers prospects for scalable preparation of highly active electrocatalysts.

Impact of climate change and human activities on the spatiotemporal dynamics of surface water area in Gansu Province, China

Understanding the dynamics of surface water area and their drivers is crucial for human survival and ecosystem stability in inland arid and semi-arid areas.This study took Gansu Province,China,a typical area with complex terrain and variable climate,as the research subject.Based on Google Earth Engine,we used Landsat data and the Open-surface Water Detection Method with Enhanced Impurity Control method to monitor the spatiotemporal dynamics of surface water area in Gansu Province from 1985 to 2022,and quantitatively analyzed the main causes of regional differences in surface water area.The findings revealed that surface water area in Gansu Province expanded by 406.88 km2 from 1985 to 2022.Seasonal surface water area exhibited significant fluctuations,while permanent surface water area showed a steady increase.Notably,terrestrial water storage exhibited a trend of first decreasing and then increasing,correlated with the dynamics of surface water area.Climate change and human activities jointly affected surface hydrological processes,with the impact of climate change being slightly higher than that of human activities.Spatially,climate change affected the'source'of surface water to a greater extent,while human activities tended to affect the'destination'of surface water.Challenges of surface water resources faced by inland arid and semi-arid areas like Gansu Province are multifaceted.Therefore,we summarized the surface hydrology patterns typical in inland arid and semi-arid areas and tailored surface water'supply-demand'balance strategies.The study not only sheds light on the dynamics of surface water area in Gansu Province,but also offers valuable insights for ecological protection and surface water resource management in inland arid and semi-arid areas facing water scarcity.

Nano surface engineering and remanufacture engineering

Nano surface engineering and remanufacture engineering are introduced, and the relationship between them is set forth. It points out the superiority of nano surface engineering to the traditional one, and reveals the advantages of remanufacture engineering. Taking some nano surface techniques as samples, such as nano-materials brush electroplating, nano-materials thermal spraying and nano-materials self-repairing antifriction additive technology, it shows the applications of nano surface engineering technology to remanufacturing mechanical parts.

Intermolecular and Surface Interactions in Engineering Processes

Interactions involving chemical reagents,solid particles,gas bubbles,liquid droplets,and solid surfaces in complex fluids play a vital role in many engineering processes,such as froth flotation,emulsion and foam formation,adsorption,and fouling and anti-fouling phenomena.These interactions at the molecular,nano-,and micro scale significantly influence and determine the macroscopic performance and efficiency of related engineering processes.Understanding the intermolecular and surface interactions in engineering processes is of both fundamental and practical importance,which not only improves production technologies,but also provides valuable insights into the development of new materials.In this review,the typical intermolecular and surface interactions involved in various engineering processes,including Derjaguin–Landau–Verwey–Overbeek(DLVO)interactions(i.e.,van der Waals and electrical doublelayer interactions)and non-DLVO interactions,such as steric and hydrophobic interactions,are first introduced.Nanomechanical techniques such as atomic force microscopy and surface forces apparatus for quantifying the interaction forces of molecules and surfaces in complex fluids are briefly introduced.Our recent progress on characterizing the intermolecular and surface interactions in several engineering systems are reviewed,including mineral flotation,petroleum engineering,wastewater treatment,and energy storage materials.The correlation of these fundamental interaction mechanisms with practical applications in resolving engineering challenges and the perspectives of the research field have also been discussed.

Surface/interface engineering of high-efficiency noble metal-free electrocatalysts for energy-related electrochemical reactions

To date,much efforts have been devoted to the high-efficiency noble metal-free electrocatalysts for hydrogen-and oxygen-involving energy conversion reactions,due to their abundance,low cost and nultifunctionally.Surface/interface engineering is found to be effective in achieving novel physicochemical properties and synergistic effects in nanomaterials for electrocatalysis.Among various engineering strategies,heteroatom-doping has been regarded as a most promising method to improve the electrocatalytic performance via the regulation of electronic structure of catalysts,and numerous works were reported on the synthesis method and mechanism investigation of heteroatom-doping electrocatalysts,though the heteroatom-doping can only provide limited active sites.Engineering of other defects such as vacancies and edge sites and construction of heterostructure have shown to open up a potential avenue for the development of noble metal-free electrocatalysts.In addition,surface functionalization can attach various molecules onto the surface of materials to easily modify their physical or chemical properties,being as a promising complement or substitute for offering materials with catalytic properties.This paper gives the insights into the diverse strategies of surface/interface engineering of the highefficiency noble metal-free electrocatalysts for energy-related electrochemical reactions.The significant advances are summarized.The unique advantages and mechanisms for specific applications are highlighted.The current challenges and outlook of this growing field are also discussed.

Attapulgite nanorods assisted surface engineering for separator to achieve high-performance lithium–sulfur batteries

Lithium-sulfur(Li-S)batteries have been recognized as one of the most promising candidates for nextgeneration portable electronic devices,owing to their extremely high energy density and low cost.However,the dissolution of lithium polysulfides(LiPSs)and consequent"shuttle effect"seriously hinder the practical deployment of Li-S batteries.Herein,multi-metal oxide nanorods named attapulgite are proposed as multifunctional ionic sieve to immobilize LiPSs and further promote the regulation of LiPSs.Attapulgite,consisting of Al,Mg,Fe,Si and O ions,possesses more polar sites to immobilize LiPSs in comparison with single metal oxides.In addition,the catalytic nature(Fe ions)of attapulgite avails the LiPSs conversion reaction,which is further confirmed by the linear sweep voltammetry and electrochemical impedance spectroscopy.Benefited from the synergistic effect of multi-metal oxide and conductive carbon,the Li-S battery with the modified separator delivers remarkable discharge capacities of 1059.4 mAh g-1 and 792.5 mAh g-1 for the first and 200th cycle at 0.5 C,respectively.The work presents an effective way to improve the electrochemical performance of Li-S batteries by employing attapulgite nanorods assisted separator surface engineering.

Atomic-level insights into surface engineering of semiconductors for photocatalytic CO_(2) reduction

Photocatalytic conversion of CO_(2)into solar fuels provides a bright route for the green and sustainable development of human society.However,the realization of efficient photocatalytic CO_(2)reduction reaction(CO_(2)RR)is still challenging owing to the sluggish kinetics or unfavorable thermodynamics for basic chemical processes of CO_(2)RR,such as adsorption,activation,conversion and product desorption.To overcome these shortcomings,recent works have demonstrated that surface engineering of semiconductors,such as introducing surface vacancy,surface doping,and cocatalyst loading,serves as effective or promising strategies for improved photocatalytic CO_(2)RR with high activity and selectivity.The essential reason lies in the activation and reaction pathways can be optimized and regulated through the reconstruction of surface atomic and electronic structures.Herein,in this review,we focus on recent research advances about rational design of semiconductor surface for photocatalytic CO_(2)RR.The surface engineering strategies for improved CO_(2)adsorption,activation,and product selectivity will be reviewed.In addition,theoretical calculations along with in situ characterization techniques will be in the spotlight to clarify the kinetics and thermodynamics of the reaction process.The aim of this review is to provide deep understanding and rational guidance on the design of semiconductors for photocatalytic CO_(2)RR.

METHOD TO EXTRACT BLEND SURFACE FEATURE IN REVERSE ENGINEERING

A new method of extraction of blend surface feature is presented. It contains two steps: segmentation and recovery of parametric representation of the blend. The segmentation separates the points in the blend region from the rest of the input point cloud with the processes of sampling point data, estimation of local surface curvature properties and comparison of maximum curvature values. The recovery of parametric representation generates a set of profile curves by marching throughout the blend and fitting cylinders. Compared with the existing approaches of blend surface feature extraction, the proposed method reduces the requirement of user interaction and is capable of extracting blend surface with either constant radius or variable radius. Application examples are presented to verify the proposed method.

Ion sulphuration-an effective surface engineering technique for reducing friction and wear of rubbing-pairs

The low temperature ion sulphuration-an effective surface engineering technique for reducing friction and wear of rubbing-pairs was introduced. It involves the principle of ion sulphuration process, microstructure of FeS film on 1045 steel, tribological properties of FeS film on steels, microstructions and tribological properties of MoS2 and nano-FeS/MoS2 multi-layered films, as well as their applications.

Machining the Integral Impeller and Blisk of Aero-Engines:A Review of Surface Finishing and Strengthening Technologies

The integral impeller and blisk of an aero-engine are high performance parts with complex structure and made of difficult-to-cut materials. The blade surfaces of the integral impeller and blisk are functional surfaces for power transmission, and their surface integrity has signif- icant effects on the aerodynamic efficiency and service life of an aero-engine. Thus, it is indispensable to finish and strengthen the blades before use. This paper presents a comprehensive literature review of studies on finishing and strengthening technologies for the impeller and blisk of aero-engines. The review includes independent and inte- grated finishing and strengthening technologies and dis- cusses advanced rotational abrasive flow machining with back-pressure used for finishing the integral impeller and blisk. A brief assessment of future research problems and directions is also presented.

Awakening the oxygen evolution activity of MoS_(2) by oxophilic-metal induced surface reorganization engineering

Although molybdenum disulfide (MoS_(2))-based materials are generally known as active electrocatalysts for the hydrogen evolution reaction (HER), the inert performance for the oxygen evolution reaction (OER) seriously limits their wide applications in alkaline electrolyzers due to there exists too strong metal-sulfur (M−S) bond in MoS_(2). Herein, by means of surface reorganization engineering of bimetal Al, Co-doped MoS_(2) (devoted as AlCo_(3)-MoS_(2)) through in situ substituting partial oxidation, we successfully significantly activate the OER activity of MoS_(2), which affords a considerably low overpotential of 323 mV at −30 mA cm^(−2), far lower than those of MoS_(2), Al-MoS_(2) and Co-MoS_(2) catalysts. Essentially, the AlCo_(3)-MoS_(2) substrate produces lots of M−O (M=Al, Co and Mo) species with oxygen vacancies, which trigger the surface self-reconstruction of pre-catalysts and simultaneously boost the electrocatalytic OER activity. Moreover, benefiting from the moderate M−O species formed on the surface, the redistribution of surface electron states is induced, thus optimizing the adsorption of OH* and OOH* intermediates on metal oxyhydroxides and awakening the OER activity of MoS_(2).

A Neural Network Approach on Reverse Engineering Surface Reasoning in the Manufacturing Field

This paper applied the neural network technology to surface reasoning in reverse engineering and established the neural network computation model. One of the main advantages of reasoning solid surface using neural network is that no knowledge about surface is needed, and the limited measured points on the surface will do sufficiently. This paper listed the related reasoning cases, including the elementary analytical surfaces and freeform surfaces, discussed the various issues occurring during reasoning process and proved the feasibility and efficiency of this approach from theory and practical computing cases. The results show that a neural network is an excellent aided analysis means for surface reasoning in reversing engineering and possesses practical use for the surface that is complex, incomplete and partially worn out or damaged.

Taking UP Challenges to Surface Engineering by Sci-Tech Advance(Continued)

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Nano Surface Engineering in the 21^(st) Century

Nano surface engineering is the new development of surface engineering, and is the typical representation that the advanced nano technology improves the traditional surface engineering. The connotation of nano surface engineering is profound. The initial stage of nano surface engineering is realized at present day. The key technologies of nano surface engineering are the support to the equipment remanufacturing. Today the relatively mature key technologies are: nano thermal spraying technology, nano electric-brush plating technology, nano self-repairing anti-friction technology and metal surface nanocrystallization, etc. Many scientific issues have been continuously discovered. Meanwhile they have been applied in the practice more and more, and have archived the excellent remanufacturing effect.

Improving the activity and stability of Ni-based electrodes for solid oxide cells through surface engineering:Recent progress and future perspectives

Solid oxide cells(SOCs)have attracted great attention in the past decades because of their high conversion efficiency,low environmental pollution and diversified fuel options.Nickel-based catalysts are the most widely used fuel electrode materials for SOCs due to the low price and high activity.However,when hydrocarbon fuels are employed,nickel-based electrodes face serious carbon deposition challenges,leading to a rapid decline of cell performance.Great efforts have been devoted to understanding the occurrence of the coking reaction,and to improving the stability of the electrodes in hydrocarbon fuels.In this review,we summarize recent research progress of utilizing surface modification to improve the stability and activity of Ni-based electrodes for SOCs by preventing carbon coking.The review starts with a briefly introduction about the reaction mechanism of carbon deposition,followed by listing several surface modification technologies and their working principles.Then we introduce representative works using surface modification strategies to prevent carbon coking on Ni-based electrodes.Finally,we highlight future direction of improving electrode catalytic activity and anti-coking performance through surface engineering.