An active learning workflow for predicting hydrogen atom adsorption energies on binary oxides based on local electronic transfer features

Machine learning combined with density functional theory(DFT)enables rapid exploration of catalyst descriptors space such as adsorption energy,facilitating rapid and effective catalyst screening.However,there is still a lack of models for predicting adsorption energies on oxides,due to the complexity of elemental species and the ambiguous coordination environment.This work proposes an active learning workflow(LeNN)founded on local electronic transfer features(e)and the principle of coordinate rotation invariance.By accurately characterizing the electron transfer to adsorption site atoms and their surrounding geometric structures,LeNN mitigates abrupt feature changes due to different element types and clarifies coordination environments.As a result,it enables the prediction of^(*)H adsorption energy on binary oxide surfaces with a mean absolute error(MAE)below 0.18 eV.Moreover,we incorporate local coverage(θ_(l))and leverage neutral network ensemble to establish an active learning workflow,attaining a prediction MAE below 0.2 eV for 5419 multi-^(*)H adsorption structures.These findings validate the universality and capability of the proposed features in predicting^(*)H adsorption energy on binary oxide surfaces.

Adsorption Kinetic Properties of As(Ⅲ)on Synthetic Nano Fe-Mn Binary Oxides

The adsorptive removal of arsenic by synthetically-prepared nano Fe-Mn binary oxides（FM） was investigated. A novel method using potassium permanganate and ferric chloride as raw materials was used to synthesise FM. The molar ratio of Fe and Mn in the synthetic Fe-Mn binary oxides was 4 ： 3. The FM-1 and FM-2（prepared at different activation temperatures） having high specific surface areas（358.87 and 128.58 m^2/g, respectively） were amorphous and of nano particle types. The amount of arsenic adsorbed on FM-1 was higher than that adsorbed on FM-2 particles. After adsorption by FM-1, residual arsenic concentration decreased to less than 10 μg/L. The adsorption kinetics data were analyzed using different kinetic models including pseudo first-order model, pseudo second-order model, Elovich model and intraparticle diffusion model. Pseudo second-order kinetic model was the most appropriate model to describe the adsorption kinetics. The adsorption percentage of As（Ⅲ） increased in the p H range of 2–3 while it decreased with the increase of pH（ 3〈pH〈10）. The effects of coexisting anions on As（Ⅲ） removal using FM-1 and FM-2 were also studied and the order of the effects is as follows： NO_3^-, Cl-, F-〈SO_4^（2-）, HCO_3-〈H_2PO_4^-, indicating that H_2PO_4^- is the major competitor with As（Ⅲ） for adsorptive sites on the surface of the adsorbents. The higher adsorption capacity of FM-1 makes it potentially attractive adsorbent for the removal of As（Ⅲ） from groundwater.

Removal of tungsten from molybdate solution by Fe-Mn binary oxide adsorbent

Considering the different geochemical enrichment behaviors of W and Mo,Fe?Mn binary oxide(FMBO),ferric hydroxide(Fe(OH)3)and manganese dioxide(MnO2)were studied to separate W from molybdate solution,respectively.The experimental results demonstrated that Fe?Mn binary oxide(FMBO)was the most suitable adsorbent for the separation.Under a wide pH(6.9?11.3)region,more than80%W removal efficiency and less than3%Mo loss could be obtained.In addition,the Fe?Mn binary oxide adsorbent can be regenerated by treating with3mol/L NaOH,and the W adsorption efficiency was retained after five adsorption?desorption?regeneration cycles.All these indicate that the Fe?Mn binary oxides have the potential for the separation of W from molybdate solution.

Comparison Study on the Microstructure of Nanocrystalline TiO_2 in Different Ti-Si Binary Oxides

Three different Ti-Si oxide structuares, silica supported titania, silica coated titania and intimately mixed silicatitania, containing 10%-40% SiO2, were made by sol-gel process. The variations of microstructure parameters of nanocrystalline （nc） TiO2-anatase in the three kirds of binary oxides, including in-plane spacing d, cell constants （ao, co）, cell volume V, cell axial ratio co/ao and crystal grain size, were comparatively investigated by high resolution transmission electron microscopy （HRTEM） and X-ray diffraction （XRD）. It is found that the microstructure parameters vary remarkably with increasing SiO2 content and annealing temperature. Different structured Ti-Si binary oxides lead to different variation tendencies of microstructure parameters. The more SiO2 the binary oxide contains, the more lattice defects of nc TiO2-anatase appear; diffusion or migration of Si cations could be an important influential factor in the variations of microstructure. The grain size of nc TiO2 in the three kinds of binary oxides not only depends on SiO2 content and annealing temperature but also on the degree of lattice microstrain and distortion of nc TiO2-anatase. Both grain size and phase transformation of nc TiO2-anatase are effectively inhibited with increasing SiO2 content.

CO_2 methanation over TiO_2–Al_2O_3 binary oxides supported Ru catalysts

TiO_2 modified Al_2O_3 binary oxide was prepared by a wet-impregnation method and used as the support for ruthenium catalyst. The catalytic performance of Ru/TiO_2–Al_2O_3catalyst in CO_2 methanation reaction was investigated. Compared with Ru/Al_2O_3 catalyst, the Ru/TiO_2–Al_2O_3catalytic system exhibited a much higher activity in CO_2 methanation reaction. The reaction rate over Ru/TiO_2–Al_2O_3 was 0.59 mol CO_2·(g Ru)1·h-1, 3.1 times higher than that on Ru/Al_2O_3[0.19 mol CO_2·(gRu)-1·h-1]. The effect of TiO_2 content and TiO_2–Al_2O_3calcination temperature on catalytic performance was addressed. The corresponding structures of each catalyst were characterized by means of H_2-TPR, XRD, and TEM. Results indicated that the averaged particle size of the Ru on TiO_2–Al_2O_3support is 2.8 nm, smaller than that on Al_2O_3 support of 4.3 nm. Therefore, we conclude that the improved activity over Ru/TiO_2–Al_2O_3catalyst is originated from the smaller particle size of ruthenium resulting from a strong interaction between Ru and the rutile-TiO_2 support, which hindered the aggregation of Ru nanoparticles.

Understanding the catalysis of chromium trioxide added magnesium hydride for hydrogen storage and Li ion battery applications

This study explores how the chemical interaction between magnesium hydride(MgH_(2))and the additive CrO_(3) influences the hydrogen/lithium storage characteristics of MgH_(2).We have observed that a 5 wt.%CrO_(3) additive reduces the dehydrogenation activation energy of MgH_(2) by 68 kJ/mol and lowers the required dehydrogenation temperature by 80℃.CrO_(3) added MgH_(2) was also tested as an anode in an Li ion battery,and it is possible to deliver over 90%of the total theoretical capacity(2038 mAh/g).Evidence for improved reversibility in the battery reaction is found only after the incorporation of additives with MgH_(2).In depth characterization study by X-ray diffraction(XRD)technique provides convincing evidence that the CrO_(3) additive interacts with MgH_(2) and produces Cr/MgO byproducts.Gibbs free energy analyses confirm the thermodynamic feasibility of conversion from MgH_(2)/CrO_(3) to MgO/Cr,which is well supported by the identification of Cr(0)in the powder by X ray photoelectron spectroscopy(XPS)technique.Through high resolution transmission electron microscopy(HRTEM)and energy dispersive spectroscopy(EDS)we found evidence for the presence of 5 nm size Cr nanocrystals on the surface of MgO rock salt nanoparticles.There is also convincing ground to consider that MgO rock salt accommodates Cr in the lattice.These observations support the argument that creation of active metal–metal dissolved rock salt oxide interface may be vital for improving the reactivity of MgH_(2),both for the improved storage of hydrogen and lithium.

THE NEW MODEL FOR CALCULATION OF STANDARD ENTROPIES OF SOLID COMPOUNDS Ⅲ CALCULATION FOR STANDARD ENTROPIES OF SOLID BINARY OXIDES

This paper establishes a new model for calculation of the standard entropies of solid binary oxides as follows: S_(29)=27.07×Φ_1+1.120×Φ_2+n_1×k×Φ, -22.19 e.u (R=0.9960) We have invesigated 103 binary oxides. and found good agreemenl between estimated and experimental entropies.

Evidence for reversible oxygen ion movement during electrical pulsing:enabler of emerging ferroelectricity in binary oxides

Ferroelectric HfO_(2)-based materials and devices show promising potential for applications in information technology but face challenges with inadequate electrostatic control,degraded reliability,and serious variation in effective oxide thickness scaling.We demonstrate a novel interface-type switching strategy to realize ferroelectric characteristics in atomic-scale amorphous binary oxide films,which are formed in oxygen-deficient conditions by atomic layer deposition at low temperatures.This approach can avoid the shortcomings of reliability degradation and gate leakage increment in scaling polycrystalline doped HfO_(2)-based films.Using theoretical modeling and experimental characterization,we show the following.(1)Emerging ferroelectricity exists in ultrathin oxide systems as a result of microscopic ion migration during the switching process.(2)These ferroelectric binary oxide films are governed by an interface-limited switching mechanism,which can be attributed to oxygen vacancy migration and surface defects related to electron(de)trapping.(3)Transistors featuring ultrathin amorphous dielectrics,used for non-volatile memory applications with an operating voltage reduced to±1 V,have also been experimentally demonstrated.These findings suggest that this strategy is a promising approach to realizing next-generation complementary metal-oxide semiconductors with scalable ferroelectric materials.

TiO_2-Supported Binary Metal Oxide Catalysts for Low-temperature Selective Catalytic Reduction of NO_x with NH_3

Binary metal oxide（MnOx-A/TiO2）catalysts were prepared by adding the second metal to manganese oxides supported on titanium dioxide（TiO2）,where,A indicates Fe2O3,WO3,MoO3,and Cr2O3.Their catalytic activity,N2 selectivity,and SO2 poisonous tolerance were investigated.The catalytic performance at low temperatures decreased in the following order：Mn-W/TiO2〉Mn-Fe/TiO2〉Mn-Cr/TiO2〉Mn-Mo/TiO2,whereas the N2 selectivity decreased in the order：Mn-Fe/TiO2〉Mn-W/TiO2〉Mn-Mo/TiO2〉Mn-Cr/TiO2.In the presence of 0.01%SO2 and 6%H2O,the NOx conversions in the presence of Mn-W/TiO2,Mn-Fe/TiO2,or Mn-Mo/TiO2 maintain 98.5%,95.8%and 94.2%, respectively,after 8 h at 120°C at GHSV 12600 h？ 1 .As effective promoters,WO3 and Fe2O3 can increase N2 selectivity and the resistance to SO2 of MnOx/TiO2 significantly.The Fourier transform infrared（FTIR）spectra of NH3 over WO3 show the presence of Lewis acid sites.The results suggest that WO3 is the best promoter of MnOx/TiO2,and Mn-W/TiO2 is one of the most active catalysts for the low temperature selective catalytic reduction of NO with NH3.

Enhancement of the formic acid electrooxidation activity of palladium using graphene/carbon black binary carbon supports

Combinations of graphene(Gr)and carbon black(C)were employed as binary carbon supports to fabricate Pd‐based electrocatalysts via one‐pot co‐reduction with Pd2+.The electrocatalytic performance of the resulting Pd/Gr‐C catalysts during the electrooxidation of formic acid was assessed.A Pd/Gr0.3C0.7(Gr oxide:C=3:7,based on the precursor mass ratio)electrocatalyst exhibited better catalytic performance than both Pd/C and Pd/Gr catalysts.The current density generated by the Pd/Gr0.3C0.7catalyst was as high as102.14mA mgPd?1,a value that is approximately3times that obtained from the Pd/C(34.40mA mgPd?1)and2.6times that of the Pd/Gr material(38.50mA mgPd?1).The anodic peak potential of the Pd/Gr0.3C0.7was120mV more negative than that of the Pd/C and70mV more negative than that of the Pd/Gr.Scanning electron microscopy images indicated that the spherical C particles accumulated on the wrinkled graphene surfaces to form C cluster/Gr hybrids having three‐dimensional nanostructures.X‐ray photoelectron spectroscopy data confirmed the interaction between the Pd metal and the binary Gr‐C support.The Pd/Gr0.3C0.7also exhibited high stability,and so is a promising candidate for the fabrication of anodes for direct formic acid fuel cells.This work demonstrates a simple and cost‐effective method for improving the performance of Pd‐based electrocatalysts,which should have potential industrial applications.

Phase Stability, Kinetic Diagrams and Diffusion Path in High Temperature Oxidation of Binary Solid-Solution Alloys

The phase diagrams of ternary systems involving two metal components and one oxidant are considered first, the limitations to their use is discussed in relation to the high temperature oxidation of binary alloys. Kinetic diagrams, which are useful to predict the conditions for the stability of the two mutually insoluble oxides as the external scale, are then calculated on the basis of thermodynamic and kinetic data concerning both the alloys and the oxides, assuming the validity of the parabolic rate law. A combination of the two types of diagrams provides a more detail information about the oxidation behavior of binary alloys. The calculation of the diffusion paths, which relate the oxidant pressure to the composition of the system in terms of the alloy components both in the alloy and in the scale during an initial stage of the reaction in the presence of the parabolic rate law, is finally developed.

Influence of Binary Oxidant (FeCl₃:APS) Ratio on the Spectroscopic and Microscopic Properties of Poly(2,5-Dimethoxyaniline)

Poly(2,5-dimethoxyaniline) (PDMA) has been synthesized by chemical oxidative polymerization technique using varying ratio (wt/wt) of binary oxidants;ferric chloride (FeCl3) and ammonium persulfate (APS). Fourier transform infrared (FT-IR) and ultraviolet-visible (Uv-vis) spectroscopic investigations provide the evidence of the presence of both benzenoid and quinoid ring units. The thermal analysis and structural characterization data suggests that the oxidant ratio greatly controls the molecular ordering in PDMA. Surface morphology shows the existence of both amorphous and crystalline domains wherein the crystalline domain size depends on the oxidant ratio. The dc conductivity (σdc) of PDMA is also a function of binary oxidant ratio and at FeCl3:APS (50:50), it increases by two orders of magnitude. Films of PDMA synthesized using FeCl3:APS (50:50) binary oxidant exhibits a decrease in the surface current on exposure to ammonia gas.

二元磁性S_(2)O_(8)^(2-)/Fe_(3)O_(4)-ZrO_(2)固体超强酸催化合成乙酸乙酯工艺研究

以无水氯化锆、过硫酸铵、硫酸亚铁、硝酸铁为原料,采用共沉淀-浸渍法制备了二元磁性S_(2)O_(8)^(2-)/Fe_(3)O_(4)-ZrO_(2)固体酸催化剂,利用IR、XRD、BET、NH_(3)-TPD对二元磁性固体酸进行表征,并用于乙酸乙酯的合成反应。实验结果表明:催化剂制备条件为Fe_(3)O_(4)的添加量35%,过硫酸铵的浸渍浓度0.5 mol/L;适宜的酯化条件为醇酸摩尔比3∶1,酯化时间2 h,固体超强酸的用量0.5 g。以S_(2)O_(8)^(2-)/Fe_(3)O_(4)-ZrO_(2)为催化剂乙酸乙酯酯化率90.25%,重复4次后,乙酸乙酯的酯化率可达62.5%。

二元复合氧化物载体在加氢脱硫催化剂中的应用进展

加氢脱硫技术对实现劣质油品清洁化、低碳化与多元化高效利用至关重要,其关键是高性能催化剂的开发,核心之一是适宜催化剂载体材料的创新。本工作分别总结了向Al_(2)O_(3)及TiO_(2)中引入第二组元后作为加氢脱硫催化剂载体的研究进展。第二组元氧化物的引入克服了Al_(2)O_(3)载体酸类型单一及商用催化剂金属与载体间相互作用过强等缺点,同时保持了较大的比表面积;第二组元氧化物能够有效提升TiO_(2)载体材料的热稳定性及比表面积的同时调节了载体材料表面酸性等。究其原因在于第二组元的引入可显著改变Al_(2)O_(3)或TiO_(2)表面羟基环境,进而促进了活性金属前驱体在载体表面的锚定和分散,有利于更多NiMo(W)S活性相的形成,提升了催化剂的加氢脱硫性能。

铁锰二元氧化物改性粉煤灰对地下水中砷的吸附特性

在我国内陆盆地和河流三角洲广泛分布着高砷地下水,吸附法作为一种简单而高效的除砷方法得到广泛的应用,但大多数吸附材料对As(Ⅲ)的吸附能力弱于As(Ⅴ),因此开发具有氧化和吸附耦合作用的高效吸附剂具有积极意义。采用共沉淀法制备铁锰二元氧化物改性粉煤灰(FMFA),探究其对As(Ⅲ)/As(Ⅴ)的吸附性能及吸附机理;通过批实验探究FMFA对溶液中As(Ⅲ)/As(Ⅴ)的吸附性能,采用XRD、SEM、BET等表征分析其表面形貌和结构,利用XPS和FT-IR分析吸附前后FMFA表面元素和官能团变化。结果表明:铁、锰氧化物均以不定形相负载于粉煤灰表面,极大地提高了FMFA的比表面积(可达166.77 m^(2)/g),为As(Ⅲ)/As(Ⅴ)的吸附提供了更多的活性位点;FMFA在中性条件下对As(Ⅲ)和As(Ⅴ)的理论最大吸附容量分别为68.19 mg/g和24.42 mg/g,As(Ⅲ)/As(Ⅴ)的吸附等温线模型均符合Freundlich模型,As(Ⅴ)的吸附过程遵循准二级动力学模型,As(Ⅲ)的吸附过程更符合Elovich模型;在溶液初始pH=5~9范围内FMFA的稳定性较好,初始pH>9的碱性环境不利于As(Ⅴ)/As(Ⅲ)的吸附;水中常见共存含氧阴离子对As(Ⅲ)/As(Ⅴ)竞争吸附影响大小的顺序为PO_(4)^(3-)>HCO_(3)^(-)>SO_(4)^(2-);FMFA可有效去除地下水样品中的砷,且不会造成铁、锰二次污染,同时具有良好的回收再生能力;在FMFA吸附As(Ⅲ)的过程中二氧化锰主要起氧化作用,铁氧化物起吸附作用,砷通过与FMFA表面金属活性羟基配体交换形成内球络合物而被吸附。本文成功制备了可高效去除地下水中As(Ⅲ)/As(Ⅴ)的绿色经济的新型吸附剂,对保障居民饮用水安全具有重要意义。

两种形貌的高储电性能ZnCo_(2)O_(4)电极材料

由于ZnCo_(2)O_(4)具有合成方法简单、成本低廉等优点,成为超级电容器领域的一种重要电极材料.通过水热、退火两步处理,制备了两种不同形貌的ZnCo_(2)O_(4)材料,并在三电极体系中测试其超级电容器性能.结果表明,花状形貌的ZnCo_(2)O_(4)纳米片微球比纳米片状ZnCo_(2)O_(4)的性能更好.电流密度1 A·g^(-1)时,ZnCo_(2)O_(4)纳米片微球电极的比电容高达3 005.0 F·g^(-1);电流密度20 A·g^(-1)时,比电容仍能保持2150.0F·g^(-1),电容保持率为71.5%.循环充/放电10000次后,电容保持率仍达到93.8%.该ZnCo_(2)O_(4)纳米片微球电极材料在超级电容器电极领域具有良好的应用前景.

Structural and Performance Regulation of Binary Transition-Metal Oxides Toward Supercapacitors:Advances and Prospects

Binary transition-metal oxides(BTMOs)are attractive candidates for advanced supercapacitors(SCs)because of their ultrahigh specific capacitance,tunable structures as well as morphologies,and low cost.To promote the practical application of BTMOs,their structure–performance relationship and developmental bottleneck should be further understood.In this review,the crystal structures and corresponding electrochemical properties of typical BTMOs in various aqueous electrolytes are briefly introduced.Some ingenious methods for improved electric conductivity,mainly including building integrated electrodes and composites,introducing oxygen vacancy,and element doping are carefully discussed.Some practicable ideas for boosting cycle stability through avoiding or alleviating agglomeration,volume change,and dissolution are provided in detail.Finally,the existing problems and challenges for structural and performance regulation of BTMOs are generalized.This review will support valuable information for building better SCs using BTMOs.

Screening of MgO- and CeO_2-Based Catalysts for Carbon Dioxide Oxidative Coupling of Methane to C_(2+) Hydrocarbons

The catalyst screening tests for carbon dioxide oxidative coupling of methane (CO2-OCM) have been investigated over ternary and binary metal oxide catalysts. The catalysts are prepared by doping MgO- and CeO2-based solids with oxides from alkali (Li2O), alkaline earth (CaO), and transition metal groups (WO3 or MnO). The presence of the peroxide (O2-2) active sites on the Li2O2, revealed by Raman spectroscopy, may be the key factor in the enhanced performance of some of the Li2O/MgO catalysts. The high reducibility of the CeO2 catalyst, an important factor in the CO2-OCM catalyst activity, may be enhanced by the presence of manganese oxide species. The manganese oxide species increases oxygen mobility and oxygen vacancies in the CeO2 catalyst. Raman and Fourier Transform Infra Red (FT-IR) spectroscopies revealed the presence of lattice vibrations of metal-oxygen bondings and active sites in which the peaks corresponding to the bulk crystalline structures of Li2O, CaO, WO3 and MnO are detected. The performance of 5%MnO/15%CaO/CeO2 catalyst is the most potential among the CeO2-based catalysts, although lower than the 2%Li2O/MgO catalyst. The 2%Li2O/MgO catalyst showed the most promising C2+ hydrocarbons selectivity and yield at 98.0% and 5.7%, respectively.

Mineralogy of Manganese Oxide Minerals in Iron Manganese Nodules of Several Main Soils in China

X-ray diffraction and selective chemical dissolution methods were used to investigate the composition of Mn oxide minerals in Fe-Mn nodules of several main types of soils in China. The changes of relative intensity of X-ray diffraction patterns were studied both before and after chemically selective dissolution. It was found that lithiophorite was a common Mn oxide in all examined Fe-Mn nodules. Todorokite, however, was a predominant Mn oxide in Fe-Mn nodules in caf-aquic Vertisols of Linyi, Shandong Province. The Fe-Mn nodules of arp-udic Luvisols in Wuhan and Zaoyang, Hubei Province, contained birnessite and vernadite. Hollandite was found in Fe-Mn nodules of alt-udic Ferrisols of Yizhang, Hunan Province; arp-udic Luvisols of Zaoyang, Hubei Province; and cal-aquic Vertisols of Linyi, Shandong Province. The Fe-Mn nodules in alt-udic Ferrisols of Guiyang, Hunan Province, had a few coronadites. Mineralogy of Mn oxide minerals in soil Fe-Mn nodules was related to soil environment, soil types and quantities of relevant cations.

Novel synthesis of SiO_x/C composite as high-capacity lithium-ion battery anode from silica-carbon binary xerogel

Micro/nanostructured SiOx/C composite was firstly synthesized by carbothermal reduction of silica-carbon binary xerogel.The homogeneous dispersion feature of the two components in binary xerogel contributes to effectively carbothermally reduce the O/Si atomic ratio,enhancing the electrochemical activity of the SiOx component.The micron-sized SiOx/C spheres are composed of many near-spherical nanoparticles.The synthesized SiOx/C exhibits a stable and high reversible capacity of 830 m A·h·g^-1 for 100 cycles,and excellent rate-capability.The homogeneous dispersion structure of phases,the micro/nanostructure and the high electrochemical activity of SiOx component combinedly contribute the excellent electrochemical performance.