Diamond-Like Carbon Depositing on the Surface of Polylactide Membrane for Prevention of Adhesion Formation During Tendon Repair

Post-traumatic peritendinous adhesion presents a significant challenge in clinical medicine.This study proposes the use of diamond-like carbon(DLC)deposited on polylactic acid(PLA)membranes as a biophysical mechanism for anti-adhesion barrier to encase ruptured tendons in tendon-injured rats.The results indicate that PLA/DLC composite membrane exhibits more efficient anti-adhesion effect than PLA membrane,with histological score decreasing from 3.12±0.27 to 2.20±0.22 and anti-adhesion effectiveness increasing from 21.61%to 44.72%.Mechanistically,the abundant C=O bond functional groups on the surface of DLC can reduce reactive oxygen species level effectively;thus,the phosphorylation of NF-κB and M1 polarization of macrophages are inhibited.Consequently,excessive inflammatory response augmented by M1 macrophage-originated cytokines including interleukin-6(IL-6),interleukin-1β(IL-1β),and tumor necrosis factor-α(TNF-α)is largely reduced.For biocompatibility evaluation,PLA/DLC membrane is slowly absorbed within tissue and displays prolonged barrier effects compared to traditional PLA membranes.Further studies show the DLC depositing decelerates the release of degradation product lactic acid and its induction of macrophage M2 polarization by interfering esterase and PLA ester bonds,which further delays the fibrosis process.It was found that the PLA/DLC membrane possess an efficient biophysical mechanism for treatment of peritendinous adhesion.

Role of atomic transverse migration in growth of diamond-like carbon films

The growth of diamond-like carbon （DLC） films is studied using molecular dynamics simulations. The effect of impact angle on film structure is carefully studied, which shows that the transverse migration of the incident atoms is the main channel of film relaxation. A transverse-migration-induced film relaxation model is presented to elucidate the process of film relaxation which advances the original model of subplantation. The process of DLC film growth on a rough surface is also investigated, as well as the evolution of microstructure and surface morphology of the film. A preferential-to-homogeneous growth mode and a smoothing of the film are observed, which are due to the transverse migration of the incident atoms.

Improved Plasmonic Hot‑Electron Capture in Au Nanoparticle/Polymeric Carbon Nitride by Pt Single Atoms for Broad‑Spectrum Photocatalytic H_(2)Evolution

ABSTRACT Rationally designing broad-spectrum photocatalysts to harvest whole visible-light region photons and enhance solar energy conversion is a“holy grail”for researchers,but is still a challenging issue.Herein,based on the common polymeric carbon nitride(PCN),a hybrid co-catalysts system comprising plasmonic Au nanoparticles(NPs)and atomically dispersed Pt single atoms(PtSAs)with different functions was constructed to address this challenge.For the dual co-catalysts decorated PCN(PtSAs–Au_(2.5)/PCN),the PCN is photoexcited to generate electrons under UV and short-wavelength visible light,and the synergetic Au NPs and PtSAs not only accelerate charge separation and transfer though Schottky junctions and metal-support bond but also act as the co-catalysts for H_(2) evolution.Furthermore,the Au NPs absorb long-wavelength visible light owing to its localized surface plasmon resonance,and the adjacent PtSAs trap the plasmonic hot-electrons for H_(2) evolution via direct electron transfer effect.Consequently,the PtSAs–Au_(2.5)/PCN exhibits excellent broad-spectrum photocatalytic H_(2) evolution activity with the H_(2) evolution rate of 8.8 mmol g^(−1) h^(−1) at 420 nm and 264μmol g^(−1) h^(−1) at 550 nm,much higher than that of Au_(2.5)/PCN and PtSAs–PCN,respectively.This work provides a new strategy to design broad-spectrum photocatalysts for energy conversion reaction.

Single‐atomic Co‐B_(2)N_(2)sites anchored on carbon nanotube arrays promote lithium polysulfide conversion in lithium-sulfur batteries

Due to low cost,high capacity,and high energy density,lithium–sulfur(Li–S)batteries have attracted much attention;however,their cycling performance was largely limited by the poor redox kinetics and low sulfur utilization.Herein,predicted by density functional theory calculations,single‐atomic Co‐B2N2 site‐imbedded boron and nitrogen co‐doped carbon nanotubes(SA‐Co/BNC)were designed to accomplish high sulfur loading,fast kinetic,and long service period Li–S batteries.Experiments proved that Co‐B2N2 atomic sites can effectively catalyze lithium polysulfide conversion.Therefore,the electrodes delivered a specific capacity of 1106 mAh g−1 at 0.2 C after 100 cycles and exhibited an outstanding cycle performance over 1000 cycles at 1 C with a decay rate of 0.032%per cycle.Our study offers a new strategy to couple the combined effect of nanocarriers and single‐atomic catalysts in novel coordination environments for high‐performance Li–S batteries.

Dual atomic catalysts from COF-derived carbon for CO_(2)RR by suppressing HER through synergistic effects

The electrochemical carbon dioxide reduction reaction(CO_(2)RR)for highvalue-added products is a promising strategy to tackle excessive CO_(2) emissions.However,the activity of and selectivity for catalysts for CO_(2)RR still need to be improved because of the competing reaction(hydrogen evolution reaction).In this study,for the first time,we have demonstrated dual atomic catalytic sites for CO_(2)RR from a core-shell hybrid of the covalent-organic framework and the metal-organic framework.Due to abundant dual atomic sites(with CoN_(4)O and ZnN_(4) of 2.47 and 11.05 wt.%,respectively)on hollow carbon,the catalyst promoted catalysis of CO_(2)RR,with the highest Faradic efficiency for CO of 92.6%at-0.8 V and a turnover frequency value of 1370.24 h^(-1) at-1.0 V.More importantly,the activity and selectivity of the catalyst were well retained for 30 h.The theoretical calculation further revealed that CoN_(4)O was the main site for CO_(2)RR,and the activity of and selectivity for Zn sites were also improved because of the synergetic roles.

Properties of polydimethylsiloxane hydrophobic modified duplex microarc oxidation/diamond-like carbon coatings on AZ31B Mg alloy

A reliable,high-performance coating procedure was developed using PDMS to modify a duplex MAO/DLC coating on an AZ31B Mg alloy.First,the duplex MAO/DLC coating was fabricated via a combined MAO and unbalanced magnetron sputter process.Subsequently,a PDMS solution was used to modify the MAO/DLC coating via a conventional dip-coating method.The surface characteristics,bond strength,hardness,tribological behaviour,and corrosion resistance of the coated samples were evaluated via SEM,CA,Raman spectroscopy,friction and wear behaviour,polarisation curve,and NSS tests.The PDMS modification reduced the HIT of MAO/DLC coating from 15.96 to 8.34GPa;this is ascribed to the penetration of PDMS,which has good rheological properties to form a viscoelastic Si-based organic polymer layer on the MAO/DLC coating.However,the PDMS-modified MAO/DLC coating was denser,hydrophobic,and had higher bond strength compared with MAO-and MAO/DLC-coated samples.Moreover,the PDMS modification reduced the COF and wear rate of the duplex MAO/DLC coating.This indicates that the PDMS improved the tribological behaviour owing to the transferred Si oxide that originated from the Si-O network of the PDMS,as well as the low graphitisation of the DLC layer during sliding.Furthermore,the corrosion current density of the MAO/DLC-coated sample modified by PDMS for 10min decreased by two order of magnitude compared with that of the MAO/DLC-coated sample but by five orders of magnitude compared with that of the bare substrate.The NSS tests proved that the PDMS layer slowed the corrosion of the Mg alloy under long-term service,enhancing the corrosion protection efficiency.The results are attributed to the high bond strength and lubricant MAO/DLC layer,and the dual role of sealing and hydrophobicity of PDMS.Therefore,PDMS modification is promising for the fabrication of protective materials for Mg alloys that require corrosion and wear resistance.

Preparation of Diamond-like Carbon Films on the Surface of Ti Alloy by Electro-deposition

In this paper, diamond-like carbon (DLC) films were deposited on Ti alloy by electro-deposition. DLC films were brown andcomposed of the compact grains whose diameter was about 400 nm. Examined by XPS, the main composition of the filmswas carbon. In the Raman spectrum, there were a broad peak at 1350 cm^(-1) and a broad peak at 1600 cm^(-1), which indicatedthat the films were DLC films.

Studies of diamond-like carbon (DLC) films deposited on stainless steel substrate with Si/SiC intermediate layers

In this work, diamond-like carbon （DLC） films were deposited on stainless steel substrates with Si/SiC intermediate layers by combining plasma enhanced sputtering physical vapour deposition （PEUMS-PVD） and microwave electron cyclotron resonance plasma enhanced chemical vapour deposition （MW-ECRPECVD） techniques. The influence of substrate negative self-bias voltage and Si target power on the structure and nano-mechanical behaviour of the DLC films were investigated by Raman spectroscopy, nano-indentation, and the film structural morphology by atomic force microscopy （AFM）. With the increase of deposition bias voltage, the G band shifted to higher wave-number and the integrated intensity ratio ID/IG increased. We considered these as evidences for the development of graphitization in the films. As the substrate negative self-bias voltage increased, particle bombardment function was enhanced and the sp^3-bond carbon density reducing, resulted in the peak values of hardness （H） and elastic modulus （E）. Silicon addition promoted the formation of sp^3 bonding and reduced the hardness. The incorporated Si atoms substituted sp^2- bond carbon atoms in ring structures, which promoted the formation of sp^3-bond. The structural transition from C-C to C-Si bonds resulted in relaxation of the residual stress which led to the decrease of internal stress and hardness. The results of AFM indicated that the films was dense and homogeneous, the roughness of the films was decreased due to the increase of substrate negative self-bias voltage and the Si target power.

Deposition of Diamond-Like Carbon on Inner Surface by Hollow Cathode Discharge

A cylindrical hollow cathode discharge （HCD） in CH4/Ar gas mixture at pressure of 20-30 Pa was used to deposit diamond-like carbon （DLC） films on the inner surface of a stainless steel tube. The characteristics of the HCD including the voltage-current curves, the plasma im- ages and the optical emission spectrum （OES） were measured in Ar and CHn/Ar mixtures. The properties of DLC films prepared under different conditions were analyzed by means of Raman spectroscopy and scanning electron microscopy （SEM）. The results show that the electron exci- tation temperature of HCD plasma is about 2400 K. DLC films can be deposited on the inner surface of tubes. The ratio of sp3/sp2 bonds decreases with the applied voltage and the deposition time. The optimizing CH4 content was found to be around CH4/Ar =1/5 for good quality of DLC films in the present system.

Tribological properties of diamond-like carbon films deposited bv pulsed laser arc deposition

A novel method, pulsed laser arc deposition combining the advantages of pulsed laser deposition and cathode vacuum arc techniques, was used to deposit the diamond-like carbon （DLC） nanofilms with different thicknesses. Spectroscopic ellipsometer, Auger electron spectroscopy, x-ray photoelectron spectroscopy, Raman spectroscopy, atomic force microscopy, scanning electron microscopy and multi-functional friction and wear tester were employed to investigate the physical and tribological properties of the deposited films. The results show that the deposited films are amorphous and the sp2, sp3 and C-O bonds at the top surface of the films are identified. The Raman peak intensity and surface roughness increase with increasing film thickness. Friction coefficients are about 0.1, 0.15, 0.18, when the film thicknesses are in the range of 17-21 nm, 30-57 nm, 67-123 nm, respectively. This is attributed to the united effects of substrate and surface roughness. The wear mechanism of DLC films is mainly abrasive wear when film thickness is in the range of 17-41 nm, while it transforms to abrasive and adhesive wear, when the film thickness lies between 72 and 123 nm.

Single-Atom Lithiophilic Sites Confined within Ordered Porous Carbon for Ultrastable Lithium Metal Anodes

Attributing to the high specific capacity and low electrochemical reduction potential,lithium(Li)metal is regarded as the most promising anode for high-energy Li batteries.However,the growth of lithium dendrites and huge volume change seriously limit the development of lithium metal batteries.To overcome these challenges,an ordered mesoporous N-doped carbon with lithiophilic single atoms is proposed to induce uniform nucleation and deposition of Li metal.Benefiting from the synergistic effects of interconnected three-dimensional ordered mesoporous structures and abundant lithiophilic single-atom sites,regulated local current density and rapid mass transfer can be achieved,leading to the uniform Li deposition with inhibition of dendrites and buffered volume expansion.As a result,the as-fabricated anode exhibits a high CE of 99.8%for 200 cycles.A stable voltage hysteresis of 14 mV at 5 mA cm^(−2)could be maintained for more than 1330 h in the symmetric cell.Furthermore,the full cell coupled with commercial LiFePO_(4)exhibits high reversible capacity of 108 mAh g^(−1)and average Coulombic efficiency of 99.8%from 5th to 350th cycles at 1 C.The ordered mesoporous carbon host with abundant lithiophilic single-atom sites delivers new inspirations into rational design of high-performance Li metal anodes.

Influence of Microwave Power on the Properties of Hydrogenated Diamond-Like Carbon Films Prepared by ECR Plasma Enhanced DC Magnetron Sputtering

Electron cyclotron resonance （ECR） plasma was applied to enhance the direct current magnetron sputtering to prepare hydrogenated diamond-like carbon （H-DLC） films. For different microwave powers, both argon and hydrogen gas are introduced separately as the ECR working gas to investigate the influence of microwave power on the microstructure and electrical property of the H-DLC films deposited on P-type silicon substrates. A series of characterization methods including the Raman spectrum and atomic force microscopy are used. Results show that, within a certain range, the increase in microwave power affects the properties of the thin films, namely the sp3 ratio, the hardness, the nanoparticle size and the resistivity all increase while the roughness decreases with the increase in microwave power. The maximum of resistivity amounts to 1.1×10^9 Ω.cm. At the same time it is found that the influence of microwave power on the properties of H-DLC films is more pronounced when argon gas is applied as the ECR working gas, compared to hydrogen gas.

Structures of Diamond-Like Carbon Films

The structures of diamond-like carbon （DLC） films, including a-C：H, a-C, ta-C：H and ta-C films have been investigated as a random covalent network with a dense film structure. The results show that sp2 C in a-C：H and a-C films tends to form olefinic and aromatic groups while sp^3 C in ta-C：H and ta-C films tends to form single or multiple sixfold groups. The hydrogen atoms in hydrogenated DLC films contribute to stabilizing the carbon skeletal networks. The film structures are well related to their properties such as optical gaps, density and hardness. The results also indicate that the high density and the extreme hardness of ta-C films are attributed to the forming of large sp^3 C bonded sixfold groups.

Structure and Mechanical Performance of Nitrogen Doped Diamond-like Carbon Films

Nitrogen doped diamond-like carbon （DLC：N） films were prepared by electron cyclotron resonance chemical vapor deposition （ECR-CVD） on polycrystalline Si chips. Film thickness is about 50 nm. Auger electron spectroscopy （AES） was used to evaluate nitrogen content, and increasing N2 flow improved N content from 0 to 7.6%. Raman and X-ray photoelectron spectroscopy （XPS） analysis results reveal CN-sp^3C and N-sp^2C structure. With increasing the N2 flow, sp^3C decreases from 73.74% down to 42.66%, and so does N-sp^3C from 68.04% down to 20.23%. The hardness decreases from 29.18 GPa down to 19.74 GPa, and the Young＇s modulus from 193.03 GPa down to 144.52 GPa.

Fabrication of Diamond-like Carbon Films by Ion Assisted Middle Frequency Unbalanced Magnetron Sputtering

Diamond-like carbon （DLC） films are deposited by the Hall ion source assisted by the mid-frequency unbalanced magnetron sputtering technique. The effects of the substrate voltage bias, the substrate temperature, the Hall discharging current and the argon/nitrogen ratio on the DLC film＇s performance were studied. The experimental results show that the film＇s surface roughness, the hardness and the Young＇s modulus increase firstly and then decrease with the bias voltage incrementally increases. Also when the substrate temperature rises, the surface roughness of the film varies slightly, but its hardness and Young＇s modulus firstly increase followed by a sharp decrease when the temperature surpassing 120 ℃. With the Hall discharging current incrementally rising, the hardness and Young＇s modulus of the film decrease and the surface roughness of the film on 316L stainless steel firstly decreased and then remains constant.

Improvement of Thermal Stability and Tribological Performance of Diamond-Like Carbon Composite Thin Films

Diamond-like carbon (DLC) is a metastable amorphous film that exhibits unique properties. However, many limitations exist regarding the use of DLC, for example, its tribological characteristics at high temperature, as well as its limited thermal stability. In this study, silicon/oxygen and silicon/nitrogen co-incorporated diamond-like carbon (Si-O-DLC and Si-N-DLC) films are studied, taking into account the thermal stability and tribological performance of these films compared with pure DLC. All the films were prepared on Si wafers, WC-Co materials, and aluminum foils using a plasma-based ion implantation (PBII) technique using acetylene (C2H2), tetramethylsilane (TMS, Si(CH3)4), oxygen (O2) and nitrogen (N2) as plasma sources. The structure of the films was characterized using Raman spectroscopy. The thermal stability of the films was measured using thermogravimetric and differential thermal analysis (TG-DTA). The friction coefficient of the films was assessed using ball-on-disk friction testing. The results indicate that Si-N-DLC films present better thermal stability due to the presence of Si-O networks in the films. The Si-N-DLC (23 at.%Si, 8 at.%N) film was affected using thermal annealing in an air atmosphere with increasing temperature until 500°C. The film can also resist thermal shock by cycling 10 times between the various temperatures and air atmosphere until 500°C. Further, Si-O-DLC and Si-N-DLC films exhibit excellent tribological performance, especially the Si-N-DLC (23 at.%Si, 8 at.%N) film, which exhibits excellent tribological performance at 500°C in an air atmosphere. It is concluded that Si-O-DLC and Si-N-DLC films improve upon the thermal stability and tribological performance of DLC.

Metal-organic framework-based single-atom electro-/ photocatalysts: Synthesis, energy applications, and opportunities

Single-atom catalysts(SACs)have gained substantial attention because of their exceptional catalytic properties.However,the high surface energy limits their synthesis,thus creating significant challenges for further development.In the last few years,metal–organic frameworks(MOFs)have received significant consideration as ideal candidates for synthesizing SACs due to their tailorable chemistry,tunable morphologies,high porosity,and chemical/thermal stability.From this perspective,this review thoroughly summarizes the previously reported methods and possible future approaches for constructing MOF-based(MOF-derived-supported and MOF-supported)SACs.Then,MOF-based SAC's identification techniques are briefly assessed to understand their coordination environments,local electronic structures,spatial distributions,and catalytic/electrochemical reaction mechanisms.This review systematically highlights several photocatalytic and electrocatalytic applications of MOF-based SACs for energy conversion and storage,including hydrogen evolution reactions,oxygen evolution reactions,O_(2)/CO_(2)/N_(2) reduction reactions,fuel cells,and rechargeable batteries.Some light is also shed on the future development of this highly exciting field by highlighting the advantages and limitations of MOF-based SACs.

Surface properties of diamond-like carbon films prepared by CVD and PVD methods

Diamond-like carbon （DLC） films have been deposited using three different techniques： （a） electron cyclotron resonance——plasma source ion implantation, （b） low-pressure dielectric barrier discharge, （c） filtered——pulsed cathodic arc discharge, The surface and mechanical properties of these films are compared using atomic force microscopebased tests. The experimental results show that hydrogenated DLC films are covered with soft surface layers enriched with hydrogen and sp^3 hybridized carbon while the soft surface layers of tetrahedral amorphous carbon （ta-C） films have graphite-like structure, The formation of soft surface layers can be associated with the surface diffusion and growth induced by the low-energy deposition process. For typical CVD methods, the atomic hydrogen in the plasmas can contribute to the formation of hydrogen and sp^3 hybridized carbon enriched surface layers, The high-energy ion implantation causes the rearrangement of atoms beneath the surface layer and leads to an increase in film density. The ta-C films can be deposited using the medium energy carbon ions in the highly-ionized plasma.

Surface Roughness of Various Diamond-Like Carbon Films

Atomic force microscopy is used to estimate and compare the surface morphology of hydrogenated and hydrogen-free diamond-like carbon （DLC） films. The films were prepared by using DC magnetron sputtering of a graphite target, pulsed cathodic carbon arcs, electron cyclotron resonance （ECR）, plasma source ion implantation and dielectric barrier discharge （DBD）. The difference in the surface structure is presented for each method of deposition. The influences of various discharge parameters on the film surface properties are discussed based upon the experimental results. The coalescence process via the diffusion of adsorbed carbon species is responsible for the formation of hydrogen-free DLC films with rough surfaces. The films with surface roughness at an atomic level can be deposited by energetic ion impacts in a highly ionized carbon plasma. The hydrocarbon species dangling bonds created by atomic hydrogen lead to the uniform growth of at the a-C：H film surfaces of the ECR or DBD plasmas

Tailoring local structures of atomically dispersed copper sites for highly selective CO_(2) electroreduction

Atomically‐dispersed copper sites coordinated with nitrogen‐doped carbon(Cu–N–C)can provide novel possibilities to enable highly selective and active electrochemical CO_(2) reduction reactions.However,the construction of optimal local electronic structures for nitrogen‐coordinated Cu sites(Cu–N_(4))on carbon remains challenging.Here,we synthesized the Cu–N–C catalysts with atomically‐dispersed edge‐hosted Cu–N_(4) sites(Cu–N_(4)C_(8))located in a micropore between two graphitic sheets via a facile method to control the concentration of metal precursor.Edge‐hosted Cu–N_(4)C_(8) catalysts outperformed the previously reported M–N–C catalysts for CO_(2)‐to‐CO conversion,achieving a maximum CO Faradaic efficiency(FECO)of 96%,a CO current density of–8.97 mA cm^(–2) at–0.8 V versus reversible hydrogen electrode(RHE),and over FECO of 90%from–0.6 to–1.0 V versus RHE.Computational studies revealed that the micropore of the graphitic layer in edge‐hosted Cu–N_(4)C_(8) sites causes the d‐orbital energy level of the Cu atom to shift upward,which in return decreases the occupancy of antibonding states in the*COOH binding.This research suggests new insights into tailoring the locally coordinated structure of the electrocatalyst at the atomic scale to achieve highly selective electrocatalytic reactions.