Steering surface reconstruction of hybrid metal oxides for efficient oxygen evolution reaction in water splitting and zinc-air batteries

Surface reconstruction yields real active species in electrochemical oxygen evolution reaction(OER)conditions;however,rationally regulating reconstruction in a targeted manner for constructing highly active OER electrocatalysts remains a formidable challenge.Here,an electrochemical activation strategy with selective etching was utilized to guide the reconstruction process of a hybrid cobalt-molybdenum oxide(CoMoO_(4)/Co_(3)O_(4)@CC)in a favorable direction to improve the OER performance.Both in-situ Raman and multiple ex-situ characterization tools demonstrate that controlled surface reconstruction can be easily achieved through Mo etching,with the formation of a dynamically stable amorphous-crystalline heterostructure.Theoretical calculations together with experimental results reveal that the synergistic effects between amorphous CoOOH and crystalline Co_(3)O_(4) are crucial in enhancing the catalytic performance.Consequently,the reconstructed CoMoO_(4)/Co_(3)O_(4)@CC exhibits a low overpotential of 250 mV to achieve a current density of 10 mA cm^(-2) in 1 M KOH,and more importantly it can be practiced in electrolytic water splitting and rechargeable zinc-air batteries devices,achieving ultra-long stability for over 500 and 1200 h,respectively.This work provides a promising route for the construction of high-performance electrocatalysts.

Covalency competition induced selective bond breakage and surface reconstruction in manganese cobaltite towards enhanced electrochemical charge storage

Manganese cobaltite(MnCo_(2)_(4))is a promising electrode material because of its attractive redox chemistry and excellent charge storage capability.Our previous work demonstrated that the octahedrally-coordinated Mn are prone to react with the hydroxyl ions in alkaline electrolyte upon electrochemical cycling and separates on the surface of spinel to reconstruct into d-MnO_(2) nanosheets irreversibly,thus results in a change of the reaction mechanism with Kþion intercalation.However,the low capacity has greatly limited its practical application.Herein,we found that the tetrahedrally-coordinated Co_(2) þions were leached when MnCo_(2)_(4) was equilibrated in 1 mol L^(-1) HCl solution,leading to the formation of layered CoOOH on MnCo_(2)_(4) surface which is originated from the covalency competition induced selective breakage of the CoT–O bond in CoT–O–CoO and subsequent rearrangement of free Co_(6) octahedra.The as-formed CoOOH is stable upon cycling in alkaline electrolyte,exhibits conversion reaction mechanism with facile proton diffusion and is free of massive structural evolution,thus enables utilization of the bulk electrode material and realizes enhanced specific capacity as well as facilitated charge transfer and ion diffusion.In general,our work not only offers a feasible approach to deliberate modification of MnCo_(2)_(4)'s surface structure,but also provides an in-depth understanding of its charge storage mechanism,which enables rational design of the spinel oxides with promising charge storage properties.

Medical and surgical approach to ocular surface reconstruction

Ocular surface disease(OSD)can have a severe impact on patients as it can lead to visual impairment and persistent discomfort.Ocular surface reconstruction(OSR)is an approach to the management of ocular diseases that cause structural damage to the ocular surface.OSR encompasses both medical and surgical treatment options.In this review,we discuss the medical and surgical strategies used in OSR.Medical management often aims to treat tear insufficiency,inflammation,and keratinization.Surgical treatments may be employed for a variety of reasons,including failure of medical management.This may include improving the oculo-palpebral structures in order to improve lid positioning and tear film.Additional therapies focus on improving tear production,such as through salivary gland transplantation.In situations where the ocular surface is so severely damaged that there is loss of limbal stem cells,limbal stem cell transplant(LSCT)may be indicated.Other surgeries such as amniotic membrane transplant(AMT)and conjunctival flaps(CFs)can help promote corneal healing.Finally,in severe situations where the cornea is beyond salvage,corneal transplantation,such as a penetrating keratoplasty(PKP),can be considered.OSR often requires a combination of medical and surgical approaches targeted to each specific patient’s presentation in order to achieve optimal outcomes.

Etching‑Induced Surface Reconstruction of NiMoO_(4) for Oxygen Evolution Reaction

Rational reconstruction of oxygen evolution reaction(OER)precatalysts and performance index of OER catalysts are crucial but still challenging for universal water electrolysis.Herein,we develop a double-cation etching strategy to tailor the electronic structure of NiMoO_(4),where the prepared NiMoO_(4) nanorods etched by H_(2)O_(2) reconstruct their surface with abundant cation deficiencies and lattice distortion.Calculation results reveal that the double cation deficiencies can make the upshift of d-band center for Ni atoms and the active sites with better oxygen adsorption capacity.As a result,the optimized sample(NMO-30M)possesses an overpotential of 260 mV at 10 mA cm−2 and excellent long-term durability of 162 h.Importantly,in situ Raman test reveals the rapid formation of high-oxidation-state transition metal hydroxide species,which can further help to improve the catalytic activity of NiMoO_(4) in OER.This work highlights the influence of surface remodification and shed some light on activating catalysts.

Anti-Corrosion and Reconstruction of Surface Crystal Plane for Zn Anodes by an Advanced Metal Passivation Technique

For the aqueous Zn-ion battery,dendrite formation,corrosion,and interfacial parasitic reactions are major issues,which greatly inhibits their practical application.How to develop a method of Zn construction or treatment to solve these issues for Zn anodes are still great challenges.Herein,a simple and cheap metal passivation technique is proposed for Zn anodes from a corrosion science perspective.Similar to the metal anticorrosion engineering,the formed interfacial protective layer in a chemical way can sufficiently solve the corrosion issues.Furthermore,the proposed passivity approach can reconstruct Zn surface-preferred crystal planes,exposing more(002)planes and improving surface hydrophilicity,which inhibits the formation of Zn dendrites and hydrogen evolution effectively.As expected,the passivated Zn achieves outstanding cycling life(1914 h)with low voltage polarization(<40 mV).Even at 6 mA cm^(−2) and 3 mA h cm^(−2),it can achieve stable Zn deposition over 460 h.The treated Zn anode coupled with MnO_(2) cathode shows prominently reinforced full batteries service life,making it a potential Zn anode candidate for excellent performance aqueous Zn-ion batteries.The proposed passivation approach provides a guideline for other metal electrodes preparation in various batteries and establishes the connections between corrosion science and batteries.

Reconstruction and stability of Fe_(3)O_(4)(001)surface:An investigation based on particle swarm optimization and machine learning

Magnetite nanoparticles show promising applications in drug delivery,catalysis,and spintronics.The surface of magnetite plays an important role in these applications.Therefore,it is critical to understand the surface structure of Fe_(3)O_(4)at atomic scale.Here,using a combination of first-principles calculations,particle swarm optimization(PSO)method and machine learning,we investigate the possible reconstruction and stability of Fe_(3)O_(4)(001)surface.The results show that besides the subsurface cation vacancy(SCV)reconstruction,an A layer with Fe vacancy(A-layer-V_(Fe))reconstruction of the(001)surface also shows very low surface energy especially at oxygen poor condition.Molecular dynamics simulation based on the iron–oxygen interaction potential function fitted by machine learning further confirms the thermodynamic stability of the A-layer-V_(Fe)reconstruction.Our results are also instructive for the study of surface reconstruction of other metal oxides.

Surface reconstruction of Se-doped NiS_(2) enables high-efficiency oxygen evolution reaction

Surface reconstruction of electrocatalysts has been widely witnessed during the electrochemical processes.Here,NiS_(2),NiSe_(2), and Se doped NiS_(2)(Se-NiS_(2)) are fabricated for oxygen evolution reaction(OER) through a mild sulfuration and/or selenylation process of Ni(OH)_(2) supported on carbon cloth(CC).Through careful in-situ Raman spectroscopy and ex-situ X-ray photoelectron spectroscopy,surface reconstruction of NiS_(2),NiSe_(2),and Se-NiS_(2) during the OER process has been revealed.A potentialdependent study shows that Se-NiS_(2) undergoes surface evolution at lower potentials and requires the lowest potential for conversion to NiOOH as a highly OER-active species,accompanied by the leaching of SO_(4)^(2-) and SeO_(4)^(2-) that can again be adsorbed on the catalyst surface to enhance the catalytic activity.Density functional theory(DFT) calculations confirm that Se-NiS_(2) is more susceptible to surface oxidation through the OER process.Therefore,Se-NiS_(2) exhibits outstanding OER activity and stability in alkaline conditions,requiring an overpotential of 343 mV at a current density of 50 mA cm^(-2).A novel insight is provided by our work in understanding the surface reconstruction and electrocatalytic mechanism of Ni-based chalcogenides.

Unveiling the parasitic-reaction-driven surface reconstruction in Ni-rich cathode and the electrochemical role of Li_(2)CO_(3)

Nickel-rich transition-metal oxides are widely regarded as promising cathode materials for high-energydensity lithium-ion batteries for emerging electric vehicles. However, achieving high energy density in Ni-rich cathodes is accompanied by substantial safety and cycle-life obstacles. The major issues of Ni-rich cathodes at high working potentials are originated from the unstable cathode-electrolyte interface, while the underlying mechanism of parasitic reactions towards surface reconstructions of cathode materials is not well understood. In this work, we controlled the Li_(2)CO_(3) impurity content on LiNi_(0.83)Mn_(0.1)Co_(0.07)O_(2) cathodes using air, tank-air, and O_(2) synthesis environments. Home-built high-precision leakage current and on-line electrochemical mass spectroscopy experiments verify that Li_(2)CO_(3) impurity is a significant promoter of parasitic reactions on Ni-rich cathodes. The rate of parasitic reactions is strongly correlated to Li_(2)CO_(3) content and severe performance deterioration of Ni83 cathodes.The post-mortem characterizations via high-resolution transition electron microscope and X-ray photoelectron spectroscopy depth profiles reveal that parasitic reactions promote more Ni reduction and O deficiency and even rock-salt phase transformation at the surface of cathode materials. Our observation suggests that surface reconstructions have a strong affiliation to parasitic reactions that create chemically acidic environment to etch away the lattice oxygen and offer the electrical charge to reduce the valence state of transition metal. Thus, this study advances our understanding on surface reconstructions of Nirich cathodes and prepares us for searching for rational strategies.

Self-derivation and reconstruction of silver nanoparticle reinforced cobalt-nickel bimetallic hydroxides through interface engineering for overall water splitting

Designing efficient and long-lasting non-metal electrocatalysts is an urgent task for addressing the issue of kinetic hysteresis in electrochemical oxidation reactions.The bimetallic hydroxides,catalyzing the oxygen evolution reaction(OER),have significant research potential because hydroxide reconstruction to generate an active phase is a remarkable advantage.Herein,the complete reconstruction of ultrathin CoNi(OH)_(2) nanosheets was achieved by embedding Ag nanoparticles into the hydroxide to induce a spontaneous redox reaction(SRR),forming heterojunction Ag@CoNi(OH)_(2) for bifunctional hydrolysis.Theoretical calculations and in situ Raman and ex situ characterizations revealed that the inductive effect of the Ag cation redistributed the charge to promote phase transformation to highly activate Ag-modified hydroxides.The Co-Ni dual sites in Co/NiOOH serve as novel active sites for optimizing the intermediates,thereby weakening the barrier formed by OOH^*.Ag@CoNi(OH)_(2) required a potential of 1.55 V to drive water splitting at a current density of 10 mA cm^(-2),with nearly 98.6% Faraday efficiency.Through ion induction and triggering of electron regulation in the OER via the synergistic action of the heterogeneous interface and surface reconstruction,this strategic design can overcome the limited capacity of bimetallic hydroxides and bridge the gap between the basic theory and industrialization of water decomposition.

Three-Dimensional Reconstruction of Welding Pool Surface by Binocular Vision

Current research of binocular vision systems mainly need to resolve the camera’s intrinsic parameters before the reconstruction of three-dimensional(3D)objects.The classical Zhang’calibration is hardly to calculate all errors caused by perspective distortion and lens distortion.Also,the image-matching algorithm of the binocular vision system still needs to be improved to accelerate the reconstruction speed of welding pool surfaces.In this paper,a preset coordinate system was utilized for camera calibration instead of Zhang’calibration.The binocular vision system was modified to capture images of welding pool surfaces by suppressing the strong arc interference during gas metal arc welding.Combining and improving the algorithms of speeded up robust features,binary robust invariant scalable keypoints,and KAZE,the feature information of points(i.e.,RGB values,pixel coordinates)was extracted as the feature vector of the welding pool surface.Based on the characteristics of the welding images,a mismatch-elimination algorithm was developed to increase the accuracy of image-matching algorithms.The world coordinates of matching feature points were calculated to reconstruct the 3D shape of the welding pool surface.The effectiveness and accuracy of the reconstruction of welding pool surfaces were verified by experimental results.This research proposes the development of binocular vision algorithms that can reconstruct the surface of welding pools accurately to realize intelligent welding control systems in the future.

COMPLEX SURFACE RECONSTRUCTION BASED ON OBJECT-ORIENTED DEVELOPING TOOL VBA

Taking AutoCAD2000 as platform, an algorithm for the reconstruction ofsurface from scattered data points based on VBA is presented. With this core technology customerscan be free from traditional AutoCAD as an electronic board and begin to create actual presentationof real-world objects. VBA is not only a very powerful tool of development, but with very simplesyntax. Associating with those solids, objects and commands of AutoCAD 2000, VBA notably simplifiesprevious complex algorithms, graphical presentations and processing, etc. Meanwhile, it can avoidappearance of complex data structure and data format in reverse design with other modeling software.Applying VBA to reverse engineering can greatly improve modeling efficiency and facilitate surfacereconstruction.

3D surface reconstruction based on binocular vision using structured light

A 3D surface reconstruction method using a binocular stereo vision technology and a coded structured light,which combines a gray code with phase-shift has been studied.The accuracy of the 3 D surface reconstruction mainly depends on the decoding of gray code views and phase-shift views.In order to find the boundary accurately,gray code patterns and their inverses are projected onto a human eye plaster model.The period dislocation between the gray code views and the phase-shift views in the course of decoding has been analyzed and a new method has been proposed to solve it.The splicing method is based on feature points.The result of the 3D surface reconstruction shows the accuracy and reliability of our method.

Surface Reconstruction of 3D Scattered Data with Radial Basis Functions

We use Radial Basis Functions （RBFs） to reconstruct smooth surfaces from 3D scattered data. An object＇s surface is defined implicitly as the zero set of an RBF fitted to the given surface data. We propose improvements on the methods of surface reconstruction with radial basis functions. A sparse approximation set of scattered data is constructed by reducing the number of interpolating points on the surface. We present an adaptive method for finding the off-surface normal points. The order of the equation decreases greatly as the number of the off-surface constraints reduces gradually. Experimental results are provided to illustrate that the proposed method is robust and may draw beautiful graphics.

Reconstruction of B-spline surface by interpolating boundary curves and approximating inner points

In this paper, we present an algorithm for reconstruction of B-spline surface such that it interpolates the four given bound- ary curves and simultaneously approximates some given inner points. The main idea of our method is： first, we construct an initial surface which interpolates the four given boundary curves; then, while keeping the boundary control points of the initial surface un- changed, we reposition the inner control points of the surface with energy optimization method. Examples show that our algorithm is practicable and effective.

Stable cycling of LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)/lithium metal batteries enabled by synergistic tuning the surface stability of cathode/anode

Ni-rich layered oxides(LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2))show great potential in long-range and low-cost lithiumion batteries.However,due to the high surface sensitivity,their practical application is hindered by interfacial instability with electrolytes under high voltage for long cyclic life.Herein,by combining both firstprinciple calculations and time-of-flight secondary ion mass spectrometry(TOF-SIMS),a novel surface fluorinated reconstruction(SFR)mechanism is proposed to improve the interfacial stability under high voltage,which could effectively regulate the surface fluoride species to desensitize the LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)interface.We demonstrate here that by tuning the ratio of fluoride species,the LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)/Li battery could achieve excellent long-term and high voltage performance(163.5 mA h g^(-1)at 0.5 C for 300 cycles under 4.4 V),while the controlled sample decayed to 125.4 mA h g^(-1)after 300 cycles.Moreover,the favorable cross-talk effect induced by SFR further facilitates the incorporation of suitable amounts of Ni ions into the construction of stable solid electrolyte interface(SEI)layer for anode surface.Therefore,the ultra-long cycling stability under high voltage can be achieved by the robust cathode/electrolyte and Li/electrolyte interfaces,which results in excellent interfacial stability after long cycling.This work provides new insights into the surface design of cathode materials and improves the stability of the electrode-electrode interface under high voltage.

Scanning tunneling microscopy study of surface reconstruction induced by N adsorption on Cu(100) surface

The reconstructed structure of Cu （100） surface induced by atomic N adsorption is studied by using scanning tunneling microscopy （STM）. The 2D structure of copper boundary between neighbouring N covered islands is found to be sensitive to the growth conditions, e.g. N＋ bombardment time and annealing temperature. The copper boundary experiences a transition from nano-scale stripe to nano-particle when the substrate is continuously annealed at 623~K for a longer time. A well-defined copper-stripe network can be achieved by precisely controlling the growth conditions, which highlights the possibility of producing new templates for nanofabrication.

Fast Mesh Reconstruction from Single View Based on GCN and Topology Modification

3D reconstruction based on single view aims to reconstruct the entire 3D shape of an object from one perspective.When existing methods reconstruct the mesh surface of complex objects,the surface details are difficult to predict and the reconstruction visual effect is poor because the mesh representation is not easily integrated into the deep learning framework;the 3D topology is easily limited by predefined templates and inflexible,and unnecessary mesh self-intersections and connections will be generated when reconstructing complex topology,thus destroying the surface details;the training of the reconstruction network is limited by the large amount of information attached to the mesh vertices,and the training time of the reconstructed network is too long.In this paper,we propose a method for fast mesh reconstruction from single view based on Graph Convolutional Network(GCN)and topology modification.We use GCN to ensure the generation of high-quality mesh surfaces and use topology modification to improve the flexibility of the topology.Meanwhile,a feature fusion method is proposed to make full use of the features of each stage of the image hierarchically.We use 3D open dataset ShapeNet to train our network and add a new weight parameter to speed up the training process.Extensive experiments demonstrate that our method can not only reconstruct object meshes on complex topological surfaces,but also has better qualitative and quantitative results.

Surface reconstruction on stishovite SiO_2,HfO_2 and rutile TiO_2 (001)

This paper systematically investigates the surface reconstruction processes and patterns on stishovite SiO2, HfO2 and rutile TiO2 （001） by using classical molecular dynamics. It is found that these three surfaces relax instead of reconstruction at 0 K, and have little possibility to reconstruct below 40 K. Above 40 K, surface reconstructions take place as collective atomic motion which can be speeded by higher temperature or compressed strain. Several reconstruction patterns with approximate surface energies are found, and electrostatic potentials on them are also provided in comparison with possible microscopic results.

PHYSICS-BASED ILLUMINATION MODEL FOR METAL SURFACE RECONSTRUCTION IN RE

Representation of roughness is introduced and the rationality of applying thephysics-based model in RE is analyzed at first. Then the scattering theory of electromagnetic waveis simplified and deduced to a physics-based model according to the characteristics of the surfaceto be reconstructed in RE. At last, the intensity diagrams of reflected field distribution areprovided to prove the feasibility of the presented model and some spheres are rendered with thismodel.

Common (π,π) Band Folding and Surface Reconstruction in Fe As-Based Superconductors

High resolution angle-resolved photoemission spectroscopy(ARPES)measurements are carried out on CaKFe_4 As_4,KCa_2 Fe_4 As_4 F_2 and(Ba_(0.6)K_(0.4))Fe_2 As_2 superconductors.Clear evidence of band folding between the Brillouin zone center and corners with a(π,π)wave vector has been found from the measured Fermi surface and band structures in all the three kinds of superconductors.A dominant √2×√2 surface reconstruction is observed on the cleaved surface of CaKFe_4As_4 by scanning tunneling microscopy(STM)measurements.We propose that the commonly observed √2×√2 reconstruction in the FeAs-based superconductors provides a general scenario to understand the origin of the(π,π)band folding.Our observations provide new insights in understanding the electronic structure and superconductivity mechanism in iron-based superconductors.