Revealing the correlation between adsorption energy and activation energy to predict the catalytic activity of metal oxides for HMX using DFT

Traditional selection of combustion catalysis is time-consuming and labor-intensive.Theoretical calculation is expected to resolve this problem.The adsorption energy of HMX and O atoms on 13 metal oxides was calculated using DMol3,since HMX and O are key substances in decomposition process.And the relationship between the adsorption energy of HMX,O on metal oxides(TiO_(2),Al_(2)O_(3),PbO,CuO,Fe_(2)O_(3),Co_(3)O_(4),Bi_(2)O_(3),NiO)and experimental T30 values(time required for the decomposition depth of HMX to reach 30%)was depicted as volcano plot.Thus,the T30 values of other metal oxides was predicted based on their adsorption energy on volcano plot and validated by previous experimental data.Further,the adsorption energy of HMX on ZrO_(2)and MnO_(2)was predicted based on the linear relationship between surface energy and adsorption energy,and T30 values were estimated based on volcano plot.The apparent activation energy data of HMX/MgO,HMX/SnO_(2),HMX/ZrO_(2),and HMX/MnO_(2)obtained from DSC experiments are basically consistent with our predicted T30 values,indicating that it is feasible to predict the catalytic activity based on the adsorption calculation,and it is expected that these simple structural properties can predict adsorption energy to reduce the large quantities of computation and experiment cost.

Porous metal oxides in the role of electrochemical CO_(2) reduction reaction

The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.

Screening non-noble metal oxides to boost the low-temperature combustion of polyethylene waste in air

Globally,the efficient utilization of polymer wastes is one of the most important issues for current sustainable development topics.Herein,a green and efficient low-temperature combustion approach is proposed to deal with polymer wastes and recover heat energy,simultaneously alleviating the environment and energy crisis.Non-noble metal oxides(Al_(2)O_(3),Fe_(2)O_(3),NiO_(2),ZrO_(2),La_(2)O_(3)and CeO_(2)) were prepared,characterized and screened to boost the low-temperature combustion of polyethylene waste at 300℃ in air.The mass change,heat release and CO_(x) formation were studied in details and employed to evaluate the combustion rate and efficiency.It was found that CeO_(2)significantly enhanced the combustion rate and efficiency,which was respectively 2 and 7 times that of non-catalytic case.An interesting phenomenon was observed that the catalytic performance of CeO_(2) in polyethylene low-temperature combustion was significantly improved by the 7-day storage in the room environment or water treatment.XPS analysis confirmed the co-existence of Ce^(3+) and Ce^(4+) in CeO_(2),and the 7-day storage and water treatment promoted the amount of Ce^(3+),which facilitated the formation of the oxygen vacancies.That may be the reason why CeO_(2) exhibited excellent catalytic performance in polyethylene low-temperature combustion.

Metal oxides heterojunction derived Bi-In hybrid electrocatalyst for robust electroreduction of CO_(2) to formate

Electrochemical reduction of Bi-based metal oxides is regarded as an effective strategy to rationally design advanced electrocatalysts for electrochemical CO_(2)reduction reaction(CO_(2)RR).Realizing high selectivity at high current density is important for formate production,but remains challenging.Herein,the BiIn hybrid electrocatalyst,deriving from the Bi2O3/In2O3heterojunction(MOD-Biln),shows excellent catalytic performance for CO_(2)RR.The Faradaic efficiency of formate(FEHCOO-) can be realized over 90% at a wide potential window from-0.4 to-1.4 V vs.RHE,while the partial current density of formate(jHCOO-) reaches about 136.7 mA cm^(-2)at-1.4 V in flow cell without IR-compensation.In additio n,the MOD-Biln exhibits superior stability with high selectivity of formate at 100 mA cm^(-2).Systematic characterizations prove the optimized catalytic sites and interface charge transfer of MOD-Biln,while theoretical calculation confirms that the hybrid structure with dual Bi/In metal sites contribute to the optimal free energy of*H and*OCHO intermediates on MOD-Biln surface,thus accelerating the formation and desorption step of*HCOOH to final formate production.Our work provides a facile and useful strategy to develop highly-active and stable electrocatalysts for CO_(2)RR.

A Generalized Polymer Precursor Ink Design for 3D Printing of Functional Metal Oxides

Three-dimensional-structured metal oxides have myriad applications for optoelectronic devices.Comparing to conventional lithography-based manufacturing methods which face significant challenges for 3D device architectures,additive manufacturing approaches such as direct ink writing offer convenient,on-demand manufacturing of 3D oxides with high resolutions down to sub-micrometer scales.However,the lack of a universal ink design strategy greatly limits the choices of printable oxides.Here,a universal,facile synthetic strategy is developed for direct ink writable polymer precursor inks based on metal-polymer coordination effect.Specifically,polyethyleneimine functionalized by ethylenediaminetetraacetic acid is employed as the polymer matrix for adsorbing targeted metal ions.Next,glucose is introduced as a crosslinker for endowing the polymer precursor inks with a thermosetting property required for 3D printing via the Maillard reaction.For demonstrations,binary(i.e.,ZnO,CuO,In_(2)O_(3),Ga_(2)O_(3),TiO_(2),and Y_(2)O_(3)) and ternary metal oxides(i.e.,BaTiO_(3) and SrTiO_(3)) are printed into 3D architectures with sub-micrometer resolution by extruding the inks through ultrafine nozzles.Upon thermal crosslinking and pyrolysis,the 3D microarchitectures with woodpile geometries exhibit strong light-matter coupling in the mid-infrared region.The design strategy for printable inks opens a new pathway toward 3D-printed optoelectronic devices based on functional oxides.

Recent progress on transition metal oxides and carbon-supported transition metal oxides as catalysts for thermal decomposition of ammonium perchlorate

As a main oxidizer in solid composite propellants,ammonium perchlorate(AP)plays an important role because its thermal decomposition behavior has a direct influence on the characteristic of solid composite propellants.To improve the performance of solid composite propellant,it is necessary to take measures to modify the thermal decomposition behavior of AP.In recent years,transition metal oxides and carbon-supported transition metal oxides have drawn considerable attention due to their extraordinary catalytic activity.In this review,we highlight strategies to enhance the thermal decomposition of AP by tuning morphology,varying the types of metal ion,and coupling with carbon analogue.The enhanced catalytic performance can be ascribed to synergistic effect,increased surface area,more exposed active sites,and accelerated electron transportation and so on.The mechanism of AP decomposition mixed with catalyst has also been briefly summarized.Finally,a conclusive outlook and possible research directions are suggested to address challenges such as lacking practical application in actual formulation of solid composite propellant and batch manufacturing.

Role of transition metal oxides in g-C_(3)N_(4)-based heterojunctions for photocatalysis and supercapacitors

g-C_(3)N_(4) emerges as a star 2D photocatalyst due to its unique layered structure,suitable band structure and low cost.However,its photocatalytic application is limited by the fast charge recombination and low photoabsorption.Rationally designing g-C_(3)N_(4)-based heterojunction is promising for improving photocatalytic activity.Besides,g-C_(3)N_(4) exhibits great potentials in electrochemical energy storage.In view of the excellent performance of typical transition metal oxides(TMOs)in photocatalysis and energy storage,this review summarized the advances of TMOs/g-C_(3)N_(4) heterojunctions in the above two areas.Firstly,we introduce several typical TMOs based on their crystal structures and band structures.Then,we summarize different kinds of TMOs/g-C_(3)N_(4) heterojunctions,including type Ⅰ/Ⅱ heterojunction,Z-scheme,p-n junction and Schottky junction,with diverse photocatalytic applications(pollutant degradation,water splitting,CO_(2) reduction and N_(2) fixation)and supercapacitive energy storage.Finally,some promising strategies for improving the performance of TMOs/g-C_(3)N_(4) were proposed.Particularly,the exploration of photocatalysis-assisted supercapacitors was discussed.

NF_3 decomposition over some metal oxides in the absence of water

NF3 decomposition in the absence of water over Al2O3, Fe2O3, Co3O4 and NiO, and transition metal oxides （Fe203, CO3O4 and NiO） coated Al2O3 reagents was investigated. The results show that Al2O3 is an active reagent for NF3 decomposition with 100% conversion lasting for 8.5 h at 400 ℃. Fe203, Co3O4 and NiO coated Al2O3 reagents are superior to bare Al2O3, and 5%Co3O4/Al2O3 has a high reactivity with NF3 full conversion maintaining for 10.5 h. It is suggested that the presence of transition metal oxide is beneficial to the reactivity of Al2O3, and results in a significant enhancement in the fluorination of Al2O3.

Effect of Crystallinity on Electrochemical Insertion/Extraction of Li in Transition Metal Oxides Part I: LiMn_2O_4 and LiCo_(0.5)Ni_(0.5)O_2

Electrochemical insertion/extraction of Li on cathode materials of spinel type LiMn2O4 and ordered rock-salt type LiCo0.5 Ni0.5O2 was measured on samples of which structures were well characterized. On the basis of experimental results on structure, morphology and charge-discharge characteristics, the effect of crystallinity of the cathode materiaIs on electrochemical Li insertion/extraction performance was discussed. These two transition metal oxides belong to onegroup that the crystallinity of these oxides affects to the performance.

Heterogeneous catalytic partial oxidation of lower alkanes(C_1–C_6) on mixed metal oxides

This review paper aims at analysing the state of the art for partial oxidation and oxidative dehydrogenation（ODH） reactions of lower alkanes C–Cinto olefins and oxygenated products（aldehydes, anhydrides,carboxylic acids） on metal oxide catalysts with cations of variable oxidation state, such as Mo and V in particular. Key parameters to be met by the catalysts, such as their redox properties, their structural aspects, active sites composed of ensembles of atoms isolated one from the others, mechanisms of reactions, are discussed. Main features of the different reactions of C–Calkanes and catalysts are analysed and their generalisation for determining more active and more selective catalysts is attempted. Prospective views for the future of the domain are proposed.

Effect of Crystallinity on Electrochemical Insertion/Extraction of Li in Transition Metal Oxides Part Ⅱ: TiO_2, V_2O_5 and MoO_3

Electrochemical insertion/extraction of Li on cathode materials of anatase type TiO_2, quasilayered structure V_2O_5 and layered structure MoO_3 was measured on samples of which structures were well characterized and showed a wide range of crystallinity. On the basis of experimental results on structure, morphology and charge-discharge characteristics, the effect of crystallinity of the cathode materials on electrochemical Li insertion/extraction pedermance was discussed. These three transition metal oxides were classified as one group on the basis of whether the crystallinity of these oxides affects to the performance or not; LiMn_2O_4 and LiCo_(0.5)O_2 belongs to the former group and TiO_2, V_2O_5 and MoO_3 to the latter.

Catalysis of Active Carbon Supporting Transition Metal Oxides for Pyrotechnical Reagent with Potassium Perchlorate

In order to improve the pyrotechnical reagent with potassium perchlorate,composite catalyst of active carbon supporting transition metal oxides （TMO）,Fe2O3 and CuO,were prepared and added into pyrotechnical reagent with potassium perchlorate.Accelerating rate calorimeter （ARC） was used to study the catalysis of pyrotechnical reagent which is consisted of potassium perchlorate and composite catalyst.Composite catalyst of both Fe2O3 and CuO supported by active carbon can catalyze pyrotechnical reagent with potassium perchlorate.Furthermore,it can lower the apparent activation energy and accelerate the reaction with a smaller quantity than that with Fe2O3 and CuO.The maximal reaction rate of pyrotechnical reagent with potassium perchlorate mixed with Fe2O3/active carbon and CuO/active carbon is 8.31 min-1 and 9.13 min-1,which is 1.74 times and 1.91 times of pyrotechnical reagent mixed with no catalyst;time to maximal rate was 18.99 min and 1.96 min respectively,which is lower than pyrotechnical reagent mixed with no catalyst by 86.46% and 98.67% ;the apparent activation energy is 368.10 kJ·mol-1 and 325.29 kJ·mol-1,which is lower than pyrotechnical reagent mixed with no catalyst by 31.89% and 39.81% respectively.

Room-Temperature Gas Sensors Under Photoactivation:From Metal Oxides to 2D Materials

Room-temperature gas sensors have aroused great attention in current gas sensor technology because of deemed demand of cheap,low power consumption and portable sensors for rapidly growing Internet of things applications.As an important approach,light illumination has been exploited for room-temperature operation with improving gas sensor's attributes including sensitivity,speed and selectivity.This review provides an overview of the utilization of photoactivated nanomaterials in gas sensing field.First,recent advances in gas sensing of some exciting different nanostructures and hybrids of metal oxide semiconductors under light illumination are highlighted.Later,excellent gas sensing performance of emerging two-dimensional materialsbased sensors under light illumination is discussed in details with proposed gas sensing mechanism.Originated impressive features from the interaction of photons with sensing materials are elucidated in the context of modulating sensing characteristics.Finally,the review concludes with key and constructive insights into current and future perspectives in the light-activated nanomaterials for optoelectronic gas sensor applications.

MICROSTRUCTURE AND INFRARED EMISSIVITY AT NORMAL TEMPERATURE IN TRANSITIONAL METAL OXIDES SYSTEM CERAMICS

The fabrication of Fe2O3-MnO2-Co2O3-CuO system ceramics, and the composite system ceramics of transitional metal oxides-cordierite and transitional metal oxides-kaolinit are presented in this work. The research was carried out with the main attention to the infrared emissivity in the band of 8 similar to 14 mu m at room temperature, the microstructure of the ceramics and the relation between them. High infrared emissivities exceeding 0.9 in the band of 8 similar to 14 mu m at room temperature were gained in the transitional metal oxide ceramics and the composite system ceramics. It is suggested that the formation of inverse spinels and partially inverse spinels, such as Fe3O4, CoFe2O4, CuFe2O4 and CuMn2O4, is beneficial to the enhancement of the infrared emissivity of the transitional metal oxide ceramics. The transitional metal oxides play an important role in determining the infrared emissivity of the composite system ceramics.

Transformation of methane to synthesis gas over metal oxides without using catalyst

This article reviews a new developing method in the field of metal oxide reduction in chemical and metallurgical processes, which uses methane as a reducing agent. Commonly, coal is used as the reducing agent in the reduction of metal oxide and other inorganic materials; Metal producing factories are among the most intensive and concentrated source of greenhouse gases and other pollutants such as heavy metals, sulfur dioxide and fly ash. Thermodynamically, methane has a great reducing capability and can be activated to produce synthesis gas over a metal oxide as an oxygen donor. Metal oxide reduction and methane activation, two concurrent thermochemical processes, can be combined as an efficient and energy-saving process; nowadays this kind of technologies is of great importance. This new reduction process could improve energy efficiencies and significantly decrease greenhouse gas emission compared to the conventional process; furthermore, the produced gases are synthesis gas that is more valuable than methane. In this paper, thermodynamic studies and advantages of this promising method were discussed. The major aim of this article is to introduce methane as a best and environmentally friendly reducing agent at low temperature.

Bifunctional nanozyme activities of layered double hydroxide derived Co-A1-Ce mixed metal oxides for antibacterial application

Marine biofouling is an expensive problem that needs evolved chemical or physical antifouling strategies.However,most of the current antifouling materials that would damage the environment through metal leaching and bacteria resistance are being halted.Nanozyme is one kind of environmental antifouling materials through generating reactive oxygen species(ROS).We prepared various contents of CeO2 that could uniform disperse compounding with Co3 O4 and CoAl2 O4 to form a stable Co-Al-Ce mixed metal oxide(MMO) by a layered double hydroxide derived method.We find that coupling with CeO2 can improve the peroxidase(POx) activity.When the molar ratio of Ce is 2.5% and the calcination temperature is 200℃,the POx activity of Co-Al-Ce MMO is the best caused by the good dispersion of catalytically active components and the high specific area(150.10±4.95 m2/g).This novel Co-Al-Ce MMO also exhibits an antibacterial mode of action Gram-negative bacteria in near-neutral pH solution through generating ROS(mainly ·O2-)in the presence of H2 O2.Ce containing MMO can be utilized as potential green marine antifouling material.

Protonated and layered transition metal oxides as solid acids for dehydration of biomass-based fructose into 5-hydroxymethylfurfural

A serial of protonated and layered transition metal oxides, including layered HTaWO6, HNbMoO6 as well as HNbWO6, were synthesized by solid-state reaction and ion-exchange. The layered HTaWO6 has been systematically studied as a solid acid to realize the dehydration of fructose to 5-hydroxymethylfurfural (HMF). The transition metal oxide samples were characterized with ICP-OES, EDS, XRD, XPS, SEM, TGA, FT-IR, N-2 adsorption-desorption and NH3-TPD. The influential factors such as reaction temperature, reaction time, solvent, catalyst amount and substrate concentration were deeply investigated. The optimized fructose conversion rate of 99% with HMF yield of 67% were achieved after 30 min at 140 degrees C in dimethylsulfoxide. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

Manipulation and Separation of Particles of Metal Oxides by Dielectrophoresis

With the development of nanotecbnology, the separation and manipulation of micro-nano-panicles have become a research focus in the field of nano-materials, nielectrophoresis（DEP） is a non-contact technology for the separation and manipulation of micro-nano-particles. Here is reported the design and fabrication of a DEP based microchip with microelectrode arrays for capturing micro-particles of inorganic oxides in petroleum. The DEP behavior of micro-particles of inorganic oxides in oil media was explored via this microchip. The microchip shows relatively a good DEP response to inorganic oxides in oil media. Furthermore, much more factors were explored such as fiequency（Hz）, and particle size（μm）, as well as metal valence. As a conclusion, the best frequency is 50 Hz. It is expected to capture panicles with different sizes or separate different oxide panicles by regulating DEP conditions. Thus, a new method could be established for the separation and purification panicles of different oxides, as well as the separation and manipulation of an oxide with different particle sizes.