Strong synergy between physical and chemical properties:Insight into optimization of atomically dispersed oxygen reduction catalysts

Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.

Atomically Dispersed Ruthenium Catalysts with Open Hollow Structure for Lithium-Oxygen Batteries

Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult decomposition of discharge products at present.Here,we have developed N-doped carbon anchored atomically dispersed Ru sites cathode catalyst with open hollow structure(h-RuNC)for Lithium–oxygen battery.On one hand,the abundance of atomically dispersed Ru sites can effectively catalyze the formation and decomposition of discharge products,thereby greatly enhancing the redox kinetics.On the other hand,the open hollow structure not only enhances the mass activity of atomically dispersed Ru sites but also improves the diffusion efficiency of catalytic molecules.Therefore,the excellent activity from atomically dispersed Ru sites and the enhanced diffusion from open hollow structure respectively improve the redox kinetics and cycling stability,ultimately achieving a high-performance lithium–oxygen battery.

Atomically dispersed Fe sites on hierarchically porous carbon nanoplates for oxygen reduction reaction

Developing cost-effective,robust and stable non-precious metal catalysts for oxygen reduction reaction(ORR) is of paramount importance for electrochemical energy conversion devices such as fuel cells and metal-air batteries.Although Fe-N-C single atom catalysts(SACs) have been hailed as the most promising candidate due to the optimal binding strength of ORR intermediates on the Fe-N_(4) sites,they suffer from serious mass transport limitations as microporous templates/substrates,i.e.,zeolitic imidazolate frameworks(ZIFs),are usually employed to host the active sites.Motivated by this challenge,we herein develop a hydrogen-bonded organic framework(HOF)-assisted pyrolysis strategy to construct hierarchical micro/mesoporous carbon nanoplates for the deposition of atomically dispersed Fe-N_(4) sites.Such a design is accomplished by employing HOF nanoplates assembled from 2-aminoterephthalic acid(NH_(2)-BDC) and p-phenylenediamine(PDA) as both soft templates and C,N precursors.Benefitting from the structural merits inherited from HOF templates,the optimized catalyst(denoted as Fe-N-C SAC-950) displays outstanding ORR activity with a high half-wave potential of 0.895 V(vs.reversible hydrogen electrode(RHE)) and a small overpotential of 356 mV at 10 mA cm^(-2) for the oxygen evolution reaction(OER).More excitingly,its application potential is further verified by delivering superb rechargeability and cycling stability with a nearly unfading charge-discharge gap of 0.72 V after 160 h.Molecular dynamics(MD) simulations reveal that micro/mesoporous structure is conducive to the rapid mass transfer of O_(2),thus enhancing the ORR performance.In situ Raman results further indicate that the conversion of O_(2) to~*O_(2)-the rate-determining step(RDS) for Fe-N-C SAC-950.This work will provide a versatile strategy to construct single atom catalysts with desirable catalytic properties.

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

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

Oxygen‑Coordinated Single Mn Sites for Efficient Electrocatalytic Nitrate Reduction to Ammonia

Electrocatalytic nitrate reduction reaction has attracted increasing attention due to its goal of low carbon emission and environmental protection.Here,we report an efficient NitRR catalyst composed of single Mn sites with atomically dispersed oxygen(O)coordination on bacterial cellulose-converted graphitic carbon(Mn-O-C).Evidence of the atomically dispersed Mn-(O-C_(2))_(4)moieties embedding in the exposed basal plane of carbon surface is confirmed by X-ray absorption spectroscopy.As a result,the as-synthesized Mn-O-C catalyst exhibits superior NitRR activity with an NH_(3)yield rate(RNH_(3))of 1476.9±62.6μg h^(−1)cm^(−2)at−0.7 V(vs.reversible hydrogen electrode,RHE)and a faradaic efficiency(FE)of 89.0±3.8%at−0.5 V(vs.RHE)under ambient conditions.Further,when evaluated with a practical flow cell,Mn-O-C shows a high RNH_(3)of 3706.7±552.0μg h^(−1)cm^(−2)at a current density of 100 mA cm−2,2.5 times of that in the H cell.The in situ FT-IR and Raman spectroscopic studies combined with theoretical calculations indicate that the Mn-(O-C_(2))_(4)sites not only effectively inhibit the competitive hydrogen evolution reaction,but also greatly promote the adsorption and activation of nitrate(NO_(3)^(−)),thus boosting both the FE and selectivity of NH_(3)over Mn-(O-C_(2))_(4)sites.

The penetration depth of atomic radicals in tubes with catalytic surface properties

Catalysis of molecular radicals is often performed in interesting experimental configurations.One possible configuration is tubular geometry.The radicals are introduced into the tubes on one side,and stable molecules are exhausted on the other side.The penetration depth of radicals depends on numerous parameters,so it is not always feasible to calculate it.This article presents systematic measurements of the penetration depth of oxygen atoms along tubes made from nickel,cobalt,and copper.The source of O atoms was a surfatron-type microwave plasma.The initial density of O atoms depended on the gas flow and was 0.7×10^(21)m^(-3),2.4×10^(21)m^(-3),and 4.2×10^(21)m^(-3)at the flow rates of 50,300,and 600 sccm,and pressures of 10,35,and 60 Pa,respectively.The gas temperature remained at room temperature throughout the experiments.The dissociation fraction decreased exponentially along the length of the tubes in all cases.The penetration depths for well-oxidized nickel were 1.2,1.7,and 2.4 cm,respectively.For cobalt,they were slightly lower at 1.0,1.3,and 1.6 cm,respectively,while for copper,they were 1.1,1.3,and 1.7 cm,respectively.The results were explained by gas dynamics and heterogeneous surface association.These data are useful in any attempt to estimate the loss of molecular fragments along tubes,which serve as catalysts for the association of various radicals to stable molecules.

Ultrafine ordered L1_(2)-Pt-Co-Mn ternary intermetallic nanoparticles as high-performance oxygen-reduction electrocatalysts for practical fuel cells

The long-range periodically ordered atomic structures in intermetallic nanoparticles(INPs)can significantly enhance both the electrocatalytic activity and electrochemical stability toward the oxygen reduction reaction(ORR)compared to the disordered atomic structures in ordinary solid-solution alloy NPs.Accordingly,through a facile and scalable synthetic method,a series of carbon-supported ultrafine Pt_3Co_(x)Mn_(1-x)ternary INPs are prepared in this work,which possess the"skin-like"ultrathin Pt shells,the ordered L1_(2) atomic structure,and the high-even dispersion on supports(L1_(2)-Pt_3Co_(x)Mn_(1-x)/~SPt INPs/C).Electrochemical results present that the composition-optimized L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C exhibits the highest electrocata lytic activity among the series,which are also much better than those of the pristine ultrafine Pt/C.Besides,it also has a greatly enhanced electrochemical stability.In addition,the effects of annealing temperature and time are further investigated.More importantly,such superior ORR electrocatalytic performance of L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C are also well demonstrated in practical fuel cells.Physicochemical characterization analyses further reveal the major origins of the greatly enhanced ORR electrocata lytic performance:the Pt-Co-Mn alloy-induced geometric and ligand effects as well as the extremely high L1_(2) atomic-ordering degree.This work not only successfully develops a highly active and stable ordered ternary intermetallic ORR electrocatalyst,but also elucidates the corresponding"structure-function"relationship,which can be further applied in designing other intermetallic(electro)catalysts.

优化污泥回流方式对多级AO-MBR工艺的影响

采用处理水量为0.15 m^(3)/h的中试装置,开展多级AO-MBR工艺处理低C/N城市污水试验研究,通过优化污泥回流方式、溶解氧及污泥浓度控制等措施,降低高溶解氧污泥回流对前端生化池的影响,实现出水水质达到地表水准Ⅳ类标准(TN除外)。结果表明,在耦合MBR工艺的形式下,经过生化池多级回流能显著保证各反应区的溶解氧环境,保持各反应区的污泥浓度平衡,进一步提高出水水质。在水温低于12℃、进水TN质量浓度为23~33 mg/L时,采用回流方式4能稳定保证TN去除率达到60%以上,实现出水TN质量浓度达到10 mg/L左右;进水TP质量浓度为2~4 mg/L时,TP去除率达到85%以上,实现出水TP质量浓度低于0.3 mg/L的要求。

改良多级AO-MBR工艺在高标准排放生活污水中的应用

针对北京农村生活污水高排放标准的要求,选用改良多级AO-MBR工艺,采用多级缺氧均匀配水进行碳源合理分配,控制好氧池DO质量浓度为0.5~1mg/L,并在工艺前端增设消氧池,MBR池300%混合液回流到首端消氧池,考察改良工艺处理农村生活污水实际运行效果。结果表明,改良工艺对COD,NH_(3)-N,TN,TP,SS的去除效率分别为94.1%,97.8%,90.0%,96.4%,98.7%,对生活污水的处理效果好、脱氮效率高且无需投加碳源,可为多级AO工艺应用设计提供新的思路。

一种改良AO技术在污水处理工程中的应用研究

通过对武汉市经开区一处雨污合流排水明渠污染治理工程的实践,重点展示了一种改良AO技术应用于污水处理工程,该技术理念基于“生物倍增”原理,具有:①大流量低能耗循环回流,气提混合液回流,回流比达到(1∶10)~(1∶100);②超高氧传质效率,6 m清水测试氧传质效率高达50%;③高污泥浓度,运行工况达到6~8 g/L;④低溶氧环境运行,实现0.3~0.5 mg/L,使硝化速率与反硝化速率同时达到一个极高水平。对比其他工艺,优点突出表现在:工艺流程短、布局紧凑、处理效率高、能耗低、管理和维护方便等。

Effects of Atomic Oxygen Irradiation on Transparent Conductive Oxide Thin Films

Transparent conductive oxide （TCO） thin film is a kind of functional material which has potential applications in solar cells and atomic oxygen （AO） resisting systems in spacecrafts. Of TCO, ZnO：Al （ZAO） and In2O3：Sn （ITO） thin films have been widely used and investigated. In this study, ZAO and ITO thin films were irradiated by AO with different amounts of fluence. The as-deposited samples and irradiated ones were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM） and Hall-effect measurement to investigate the dependence of the structure, morphology and electrical properties of ZAO or ITO on the amount of fluence of AO irradiation. It is noticed that AO has erosion effects on the surface of ZAO without evident influences upon its structure and conductive properties. Moreover, as the amount of AO fluence rises, the carrier concentration of ITO decreases causing the resistivity to increase by at most 21.7%.

A Simulator for Producing of High Flux Atomic Oxygen Beam by Using ECR Plasma Source

In order to study the atomic oxygen corrosion of spacecraft materials in low earth orbit environment, an atomic oxygen simulator was established. In the simulator, a 2.45 GHz microwave source with maximum power of 600 W was launched into the circular cavity to generate ECR (electron cyclotron resonance) plasma. The oxygen ion beam moved onto a negatively biased Mo plate under the condition of symmetry magnetic mirror field confine, then was neutralized and reflected to form oxygen atom beam. The properties of plasma density, electron temperature, plasma space potential and ion incident energy were characterized. The atomic oxygen beam flux was calibrated by measuring the mass loss rate of Kapton during the atomic oxygen exposure. The test results show that the atomic oxygen beam with flux of 1016-1017 atoms-cm-2·s-1 and energy of 5-30 eV and a cross section of φ80 mm could be obtained under the operating pressure of 10-1-10-3 Pa. Such a high flux source can provide accelerated simulation tests of materials and coatings for space applications.

Experimental Study of Vacuum Ultraviolet Radiation Effects and Its Synergistic Effects with Atomic Oxygen on a Spacecraft Material-Polytetrafluoroethylene

Polytetrafluoroethylene (Teflon), a widely used spacecraft material, isstudied to investigate the vacuum ultraviolet (VUV) effects and its synergistic effects with atomicoxygen (AO) in a ground-based simulation facility. The samples before and after the experiments arecompared in appearance, mass, optical properties and surface composition. The reactioncharacteristics of Teflon are summarized and the reaction mechanisms are analyzed. The followingconclusion can be drawn: at the action of VUV the Teflon sample surface is darkened for theaccumulation of carbon; and when the sample is exposed to AO, the carbon is oxidized and thedarkening surface is bleached; the synergistic effects of VUV and AO may cause the erosion of Teflonmore severe.

Active sites engineering of Pt/CNT oxygen reduction catalysts by atomic layer deposition

Understanding carbon-supported Pt-catalyzed oxygen reduction reaction(ORR)from the perspective of the active sites is of fundamental and practical importance.In this study,three differently sized carbon nanotube-supported Pt nanoparticles(Pt/CNT)are prepared by both atomic layer deposition(ALD)and impregnation methods.The performances of the catalysts toward the ORR in acidic media are comparatively studied to probe the effects of the sizes of the Pt nanoparticles together with their distributions,electronic properties,and local environments.The ALD-Pt/CNT catalysts show much higher ORR activity and selectivity than the impregnation-Pt/CNT catalysts.This outstanding ORR performance is ascribed to the well-controlled Pt particle sizes and distributions,desirable Pt^04f binding energy,and the Cl-free Pt surfaces based on the electrocatalytic measurements,catalyst characterizations,and model calculations.The insights reported here could guide the rational design and fine-tuning of carbon-supported Pt catalysts for the ORR.

Investigation of Surface Reaction and Degradation Mechanism of Kapton during Atomic Oxygen Exposure

The erosion behavior of Kapton when exposed to atomic oxygen (AO) environment in the ground-based simulation facility was studied. The chemical and physical changes of sample surfaces after exposed to AO fluxes were investigated by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results indicated that Kapton underwent dramatically degradation, including much mass loss and change of surface morphologies; vacuum outgassing effect of Kapton was the key factor for initial mass loss in the course of atomic oxygen beam exposures. XPS analysis showed that the carbonyl group in Kapton reacted with oxygen atoms to generate CO2, then CO2 desorbed from Kapton surface. In addition, PMDA in the polyimide structure degraded due to the reaction with atomic oxygen of 5 eV.

Ground-based Investigations of Atomic Oxygen Erosion Behaviors of Silver and Ion-implanted Silver

Silver foils and ion-implanted silver foils exposed to atomic oxygen （AO） generated in a ground simulation facility were investigated by the quartz crystal microbalance （QCM）, the scanning electron microscopy （SEM） and the X-ray photoelectron spectroscopy （XPS）. The experimental results show the presence of Ag2O and AgO in an oxidation process of the silver foil having exposure to AO. As soon as silver comes under the bombardment of atomic oxygen, the oxidation process starts with a thick film forming on the silver surface. Because of the development of stresses, the oxide layer gets cracked and spalled, which leads to appearance of a new silver surface intensifying further oxidation. At last, AgO begins to form on the outer surface of the oxide film. The analytical results of the XPS and the AES attest to formation of a continuous high-quality protective oxide-based layer on the surface of ion-implanted silver films after exposure to AO. This layer can well protect materials in question from erosion.

Atomically Dispersed Transition Metal-Nitrogen-Carbon Bifunctional Oxygen Electrocatalysts for Zinc-Air Batteries:Recent Advances and Future Perspectives

Rechargeable zinc-air batteries(ZABs)are currently receiving extensive attention because of their extremely high theoretical specific energy density,low manufacturing costs,and environmental friendliness.Exploring bifunctional catalysts with high activity and stability to overcome sluggish kinetics of oxygen reduction reaction and oxygen evolution reaction is critical for the development of rechargeable ZABs.Atomically dispersed metal-nitrogen-carbon(M-N-C)catalysts possessing prominent advantages of high metal atom utilization and electrocatalytic activity are promising candidates to promote oxygen electrocatalysis.In this work,general principles for designing atomically dispersed M-N-C are reviewed.Then,strategies aiming at enhancing the bifunctional catalytic activity and stability are presented.Finally,the challenges and perspectives of M-N-C bifunctional oxygen catalysts for ZABs are outlined.It is expected that this review will provide insights into the targeted optimization of atomically dispersed M-N-C catalysts in rechargeable ZABs.

Preparation and anti atomic oxygen erosion properties of OPPOSS/PI composites

Atomic oxygen （AO） found in low earth orbit can cause serious erosion to polyimide （PI） materials, which greatly limits their lifetime. 8-phenyl silsesquioxane （OPPOSS） was synthesized, and OPPOSS/PI composites were pre- pared by physical blending, followed by thermal imidization to enhance the AO erosion resistance of PI materials. The morphology, composition, and structure of the composites were analyzed before and after AO exposure in a ground sim- ulated facility of atomic oxygen. After 16 h AO exposure, the OPPOSS/PI composite with 5wt% OPPOSS addition shows an erosion rate of about 1.4×10-24 cm3/atom with only 48% mass loss of that of PI without OPPOSS addition. The mixture of OPPOSS nano molecules is assembled into a kind of regular square structure and distributed evenly in OPPOSS/PI composites. Some SiO2 particles are formed in the composites during AO exposure, which can act as ＂inert points＂ to reduce the AO erosion rate of OPPOSS/PI composites.

Resistance of Nanoclay Reinforced Epoxy Composites to Hyperthermal Atomic Oxygen Attack

Due to outstanding mechanical properties, heat resistance, and relatively facile production,nanoclay reinforced epoxy composites(NCRE composites) have been suggested as candidate materials for use on external surfaces of spacecraft residing in the low Earth orbit(LEO) environment. The resistance of the NCRE composites to bombardment by atomic oxygen(AO), a dominant component of the LEO environment, has been investigated. Four types of samples were used in this study. They were pure epoxy(0 wt% nanoclay content), and NCRE composites with different loadings of nanoclay—1 wt%, 2 wt%, and 4 wt%. Etch depths decreased with increasing nanoclay content, and for the 4 wt% samples it ranged from 28% to 37% compared to that of pure epoxy. X-ray photoelectron spectroscopy(XPS) indicates that after AO bombardment, relative area of C-C/C-H peak decreased,while the area of the C-O, ketones peaks increased, and the oxidation degree of surfaces increased. New carbon-related component carbonates were detected on nanoclay containing composite surfaces. Scanning electron microscopy indicates that aggregates formed on nanoclay-containing surfaces after AO bombardment. The sizes and densities of aggregates increased with nanoclay content. The combined erosion depths, XPS and SEM results indicate that although all the studied surfaces got eroded and oxidized after AO bombardment,the nanoclay containing composites showed better AO resistance compared to pure epoxy,because the produced aggregates on surface potentially act as a physical "shield", effectively retarding parts of the surface from further AO etching.

Atomically Dispersed Fe-N_4 Modified with Precisely Located S for Highly Efficient Oxygen Reduction

Immobilizing metal atoms by multiple nitrogen atoms has triggered exceptional catalytic activity toward many critical electrochemical reactions due to their merits of highly unsaturated coordination and strong metal-substrate interaction.Herein,atomically dispersed Fe-NC material with precise sulfur modification to Fe periphery(termed as Fe-NSC) was synthesized,X-ray absorption near edge structure analysis confirmed the central Fe atom being stabilized in a specific configuration of Fe(N3)(N-C-S).By enabling precisely localized S doping,the electronic structure of Fe-N4 moiety could be mediated,leading to the beneficial adjustment of absorption/desorption properties of reactant/intermediate on Fe center.Density functional theory simulation suggested that more negative charge density would be localized over Fe-N4 moiety after S doping,allowing weakened binding capability to *OH intermediates and faster charge transfer from Fe center to O species.Electrochemical measurements revealed that the Fe-NSC sample exhibited significantly enhanced oxygen reduction reaction performance compared to the S-free Fe-NC material(termed as Fe-NC),showing an excellent onset potential of 1.09 V and half-wave potential of 0.92 V in 0.1 M KOH.Our work may enlighten relevant studies regarding to accessing improvement on the catalytic performance of atomically dispersed M-NC materials by managing precisely tuned local environments of M-Nx moiety.