Selective oxidative dehydrogenation of ethane to ethylene over a hydroxylated boron nitride catalyst

Boron nitride containing hydroxyl groups efficiently catalysed oxidative dehydrogenation of ethane to ethylene,offering rather high selectivity（95%） but only small amount of CO2 formation（0.4%） at a given ethane conversion of 11%.Even at high conversion level of 63%,the selectivity of ethylene retained at 80%,which is competitive with the energy-demanding industrialized steam cracking route.A long-term test for 200 h resulted in stable conversion and product selectivity,showing the excellent catalytic stability.Both experimental and computational studies have identified that the hydrogen abstraction of B-OH groups by molecular oxygen dynamically generated the active sites and triggered ethane dehydrogenation.

Enhanced visible-light photocatalytic activity of Z-scheme graphitic carbon nitride/oxygen vacancy-rich zinc oxide hybrid photocatalysts

With the objectives of enhancing the stability,optical properties and visible-light photocatalytic activity of photocatalysts,we modified oxygen vacancy-rich zinc oxide（Vo-ZnO） with graphitic carbon nitride（g-C3N4）. The resulting g-C3N4/Vo-ZnO hybrid photocatalysts showed higher visible-light photocatalytic activity than pure Vo-ZnO and g-C3N4. The hybrid photocatalyst with a g-C3N4 content of 1 wt% exhibited the highest photocatalytic degradation activity under visible-light irradiation（λ≥ 400 nm）. In addition,the g-C3N4/Vo-ZnO photocatalyst was not deactivated after five cycles of methyl orange degradation,indicating that it is stable under light irradiation. Finally,a Z-scheme mechanism for the enhanced photocatalytic activity and stability of the g-C3N4/Vo-ZnO hybrid photocatalyst was proposed. The fast charge separation and transport within the g-C3N4/Vo-ZnO hybrid photocatalyst were attributed as the origins of its enhanced photocatalytic performance.

Effect of ZrO_2-nitrides Composite Powder Addition on Oxidation Resistance of Al_2O_3-C Refractories

Oxidation of carbon is the main problem or Al2O3 - C refractories. ZrO2 - nitrides composite powder was synthesized through carbothermal reduction and nitridation （CRN） of zircon. The effect of ZrO2 - nitrides composite powder addition on oxidation resistance of the Al2O3 - C refractories was investigated by measuring the thickness of oxidation layer. Phase compositions of the Al2O3 - C refractories before and after oxidation were investigated by X-ray diffraction （ XRD ）. Results show that the oxidation resistance of the Al2O3 - C refractories can be obviously improved by adding the synthesized ZrO2 - nitrides composite powder. The formation of mullite and zircon in the oxidation layer results in the densification of oxidation layer, which prevents oxygen diffusion and bnproves the oxidation resistance of the Al2O3 - C refractories.

Insight into structure evolution of carbon nitrides and its energy conversion as luminescence

A series of carbon nitride(CN)materials represented by graphitic carbon nitride(g-C_(3)N_(4))have been widely used in bioimaging,biosensing,and other fields in recent years due to their nontoxicity,low cost,and high luminescent quantum efficiency.What is more attractive is that the luminescent properties such as wavelength and intensity can be regulated by controlling the structure at the molecular level.Hence,it is time to summarize the related research on CN structural evolution and make a prospect on future developments.In this review,we first summarize the research history and multiple structural evolution of CN.Then,the progress of improving the luminescence performance of CN through structural evolution was discussed.Significantly,the relationship between CN structure evolution and energy conversion in the forms of photoluminescence,chemiluminescence,and electrochemiluminescence was reviewed.Finally,key challenges and opportunities such as nanoscale dispersion strategy,luminous efficiency improving methods,standardization evaluation,and macroscopic preparation of CN are highlighted.

Recent advances in pseudocapacitor electrode materials: Transition metal oxides and nitrides

Faraday pseudocapacitors take both advantages of secondary battery with high energy density and supercapacitors with high power density,and electrode material is the key to determine the performance of Faraday pseudocapacitors.Transition metal oxides and nitrides,as the two main kinds of pseudocapacitor electrode materials,can enhance energy density while maintaining high power capability.Recent advances in designing nanostructured architectures and preparing composites with high specific surface areas based on transition metal oxides and nitrides,including ruthenium oxides,nickel oxides,manganese oxides,vanadium oxides,cobalt oxides,iridium oxides,titanium nitrides,vanadium nitrides,molybdenum nitrides and niobium nitrides,are addressed,which would provide important significances for deep researches on pseudocapacitor electrode materials.

Theoretical insights into the structures and fundamental properties of pnictogen nitrides

Recent experimental advancements reported a chemical reaction between antimony and nitrogen under high temperature and high pressure,yielding crystalline antimony nitride(Sb_(3)N_(5))with an orthorhombic structure.Motivated by this statement,we calculate the stability,elastic properties,electronic properties and energy density of the Cmc2_(1) structure for pnictogen nitrides X_(3)N_(5)(X=P,As,Sb,and Bi)using first-principles calculations combined with particle swarm optimization algorithms.Calculations of formation enthalpies,elastic constants and phonon spectra show that P_(3)N_(5),As_(3)N_(5) and Sb_(3)N_(5) are thermodynamically,mechanically and kinetically stable at 35 GPa,whereas Bi_(3)N_(5) is mechanically and kinetically stable but thermodynamically unstable.The computed electronic density of states shows strong covalent bonding between the N atoms and the phosphorus group atoms in the four compounds,confirmed by the calculated electronic localization function.We also calculate the energy densities for Sb_(3)N_(5) and find it to be a potentially high-energy-density material.

Effect of trace oxygen on plasma nitriding of titanium foil

Titanium nitride films are prepared by plasma enhanced chemical vapor deposition method on titanium foil using N_(2) as precursor. In order to evaluate the effect of oxygen on the growth of titanium nitride films, a small amount of O_(2) is introduced into the preparation process. The study indicates that trace O_(2) addition into the reaction chamber gives rise to significant changes on the color and micro-morphology of the foil, featuring dense and long nano-wires. The as-synthesized nanostructures are characterized by various methods and identified as TiN, Ti_(2) N, and TiO_(2) respectively. Moreover, the experiment results show that oxide nanowire has a high degree of crystallinity and the nitrides present specific orientation relationships with the titanium matrix.

Synthesis of boron nitride nanorod and its performance as a metalfree catalyst for oxidative desulfurization of diesel fuel

In order to reduce the sulfur compounds in diesel fuel,boron nitride(BN)has been used as a novel metal-free catalyst in the present research.This nanocatalyst was synthesized via template-free approach followed by heating treatment at 900℃ in nitrogen atmosphere that the characteristics of the sample were identified by the X-ray diffraction,Fourier-transform infrared spectroscopy,Raman spectroscopy,field emission scanning electron microscopy,transmission electron microscopy,atomic force microscopy,and N2 adsorption-desorption isotherms.The results of structural and morphological analysis represented that BN has been successfully synthesized.The efficacy of the main operating parameters on the process was studied by using response surface methodology based on the Box-Behnken design method.The prepared catalyst showed high efficiency in oxidative desulfurization of diesel fuel with initial sulfur content of 8040 mg·kg^(-1)S.From statistical analysis,a significant quadratic model was obtained to predict the sulfur removal as a function of efficient parameters.The maximum efficiency of 72.4%was achieved under optimized conditions at oxidant/sulfur molar ratio of 10.2,temperature of 71℃,reaction time of 113 min,and catalyst dosage of 0.36 g.Also,the reusability of the BN was studied,and the result showed little reduction in activity of the catalyst after 10 times regeneration.Moreover,a plausible mechanism was proposed for oxidation of sulfur compounds on the surface of the catalyst.The present study shows that BN materials can be selected as promising metal-free catalysts for desulfurization process.

N-hydroxyphthalimide anchored on hexagonal boron nitride as a metal-free heterogeneous catalyst for deep oxidative desulfurization

A metal-free N-hydroxyphthalimide/hexagonal boron nitride(NHPI/h-BN)catalytic system was developed for deep oxidative desulfurization(ODS)of fuel oils.Detailed experiments find that the heterogenization process of loading NHPI on h-BN not only benefits to the dispersion and utilization of NHPI,but also can significantly promote the catalytic performance.By employing NHPI/h-BN as the catalyst,azodiisobutyronitrile(AIBN)as the metal-free initiator,a 95%conversion of dibenzothiophene(DBT)can be acquired under the reaction conditions of 120°C and atmospheric pressure with molecular oxygen(O_(2))as oxidant.Moreover,the heterogenization is convenient for the regeneration of the catalyst with>94%DBT conversion after being recycled seven times.Characterizations illustrate that the promoted catalytic activity along with the regenerability originate from the interactions between NHPI and h-BN.The catalytic mechanism study shows that molecular oxygen is readily activated by the NHPI/h-BN to form a superoxide radical(O_(2)^(·-)),which oxidize DBT to DBTO2 for desulfurization.

Preparation and properties of transition metal nitrides caged in N-doped hollow porous carbon sphere for oxygen reduction reaction

A series of transition metal nitrides(MxNy,M=Fe,Co,Ni)nanoparticle(NP)composites caged in N-doped hollow porous carbon sphere(NHPCS)were prepared by impregnation and heat treatment methods.These composites combine the high catalytic activity of nitrides and the high-efficiency mass transfer characteristics of NHPCS.The oxygen reduction reaction results indicate that Fe2N/NHPCS has the synergistic catalytic performance of higher onset potential(0.96 V),higher electron transfer number(~4)and higher limited current density(1.4 times as high as that of commercial Pt/C).In addition,this material is implemented as the air catalyst for zinc−air battery that exhibits considerable specific capacity(795.1 mA·h/g)comparable to that of Pt/C,higher durability and maximum power density(173.1 mW/cm2).

An efficient strategy for photocatalytic hydrogen peroxide production over oxygen-enriched graphitic carbon nitride with sodium phosphate

Photocatalytic hydrogen peroxide(H_(2)O_(2))production is a promising strategy to replace the traditional production processes;however,the inefficient H_(2)O_(2) productivity limits its application.In this study,oxygen-rich g-C_(3)N_(4) with abundant nitrogen vacancies(OCN)was synthesized for photocatalytic H_(2)O_(2) production.X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy indicated that oxygen-containing functional groups(–COOH and C–O–C)were obtained.Electron paramagnetic resonance confirmed the successful introduction of nitrogen vacancies.OCN exhibited efficient photocatalytic H_(2)O_(2) production performance of 1965μmol L^(−1) h^(−1) in air under visible-light irradiation.The high H_(2)O_(2) production was attributed to the enhanced adsorption of oxygen,enlarged specific surface area,and promoted carrier separation.An increased H_(2)O_(2) production rate(5781μmol L^(−1) h^(−1))was achieved in a Na_(3)PO_(4) solution.The improved performance was attributed to the changed reactive oxygen species.Specifically,the adsorbed PO_(4)^(3−) on the surface of the OCN promoted the transfer of holes to the catalyst surface.•O_(2)−obtained by O_(2) reduction reacted with adjacent holes to generate 1O_(2),which could efficiently generate H_(2)O_(2) with isopropanol.Additionally,PO_(4)^(3−),as a stabilizer,inhibited the decomposition of H_(2)O_(2).

Silicon Nitride Etch via Oxidation Reaction in Fluorocarbon/Oxygen Plasma:A First-Principle Study

Conducting all-in-one etch process for 3D-NAND fabrication requires close etch rate(E/R)for SiO2 and Si3N4;however,to attain comparable and high etch rate for both materials is challenging.In this work,we performed first-principle studies on the etching mechanism of Si3N4 in fluorocarbon/oxygen plasma.The feasibility of using fluorocarbon/oxygen plasma to etch Si3N4 while attaining close E/R to SiO2 through the complementary nitride to oxynitiride(SiOxNy)transformation has been identified.Such transformation involves two stages:N atom elimination and Si-O bond formation.By modeling the essential chemical reactions on the Si3N4 surface,we shed light upon the underlying mechanisms behind both stages.We simulated the N-elimination reactions involving the formation and desorption of NO and FNO molecules as well as the substitution with F atoms.We found that N atoms can be eliminated by forming NO molecules,especially with the assistance of F-substitution in Si-N bond breaking.The predicted O-additive energies indicates that forming SiOxNy structure after N-elimination is possible.Following that,the dependency of chemistries favoring either high E/R or active SiOxNy formation on the fluorocarbon/oxygen ratio was discussed.We hope that the work will build a foundation for future studies on pursuing all-in-one ON etch process via the surface modifications.

Synthesis and Characterization of Vanadium Molybdenum Oxynitrides Nanoparticles in the Channels of MCM-41

Vanadium molybdenum oxynitrides nanoparticles were synthesized successfully in the channels of MCM-41 after surface modification,vacumm co-impregnation and nitridation technology.The products were investigated by nitrogen sorption measurement,X-ray powder diffraction（XRD）,high-resolution transmission electron microscopy（HRTEM）,energy dispersive analysis of X-rays（EDAX）and CNH element analysis.The investigation resnlts show that superfine nanoparticles of vanadium molybderum oxynitrides exist in the channels of MCM-41.

Plasma-Chemical Synthesis of Nanosized Powders-Nitrides,Carbides,Oxides,Carbon Nanotubes and Fullerenes

In this article the plasma-chemical synthesis of nanosized powders （nitrides, car- bides, oxides, carbon nanotubes and fullerenes） is reviewed. Nanosized powders - nitrides, carbides, oxides, carbon nanotubes and fullerenes have been successfully produced using different techniques, technological apparatuses and conditions for their plasma-chemical synthesis.

An Efficient Boron Source Activation Strategy for the Low‑Temperature Synthesis of Boron Nitride Nanotubes

Lowering the synthesis temperature of boron nitride nanotubes(BNNTs)is crucial for their development.The primary reason for adopting a high temperature is to enable the effective activation of highmelting-point solid boron.In this study,we developed a novel approach for efficiently activating boron by introducing alkali metal compounds into the conventional MgO–B system.This approach can be adopted to form various low-melting-point AM–Mg–B–O growth systems.These growth systems have improved catalytic capability and reactivity even under low-temperature conditions,facilitating the synthesis of BNNTs at temperatures as low as 850℃.In addition,molecular dynamics simulations based on density functional theory theoretically demonstrate that the systems maintain a liquid state at low temperatures and interact with N atoms to form BN chains.These findings offer novel insights into the design of boron activation and are expected to facilitate research on the low-temperature synthesis of BNNTs.

PRODUCTION OF ULTRAFINE PARTICLES OF OXIDES AND NITRIDES BY LASER BEAMS

Ultrafine particles of Al_(2)O_(3),MoO_(3),TiO_(2)and SiO_(2)were prepared by irradiate high power laser beams on material surface in O_(2)atmosphere as well as TiN in N_(2) atmosphere.X-ray diffractometer analysis identified that all oxides and nitrides powder obtained are crystalline except SiO_(2) particles which have amorphous struc-ture.

In-situ oriented oxygen-defect-rich Mn-N-O via nitridation and electrochemical oxidation based on industrial-scale Mn_(2)O_(3) to achieve high-performance aqueous zinc ion battery

As a general problem in the field of batteries,materials produced on a large industrial scale usually possess unsatisfactory electrochemical performances.Among them,manganese-based aqueous rechargeable zinc-ion batteries(ARZBs)have been emerging as promising large-scale energy storage systems owing to their high energy densities,low manufacturing cost and intrinsic high safety.However,the direct application of industrial-scale Mn2O3(MO)cathode exhibits poor electrochemical performance especially at high current rates.Herein,a highly reversible Mn-based cathode is developed from the industrial-scale MO by nitridation and following electrochemical oxidation,which triples the ion diffusion rate and greatly promotes the charge transfer.Notably,the cathode delivers a capacity of 161 m Ah g^(-1) at a high current density of 10 A g^(-1),nearly-three times the capacity of pristine MO(60 m Ah g^(-1)).Impressive specific capacity(243.4 m Ah g^(-1))is obtained without Mn^(2+) additive added in the electrolyte,much superior to the pristine MO(124.5 m Ah g^(-1)),suggesting its enhanced reaction kinetics and structural stability.In addition,it possesses an outstanding energy output of 368.4 Wh kg^(-1) at 387.8 W kg^(-1),which exceeds many of reported cathodes in ARZBs,providing new opportunities for the large-scale application of highperformance and low-cost ARZBs.

Vanadium supported on graphitic carbon nitride as a heterogeneous catalyst for the direct oxidation of benzene to phenol

A series of graphitic carbon nitride supported vanadium catalysts（xV/g-C3N4） with different vanadium contents（x/%） were prepared by impregnation.XRD,FT-IR,TEM,TG-DTG,nitrogen adsorption and XPS characterizations were conducted which revealed a strong interaction between the vanadium species and g-C3N4 support.8V/g-C3N4 exhibited the highest activity and showed stable recyclability in the benzene hydroxylation reaction with a benzene conversion of 24.6%and phenol selectivity of 99.2%under the optimized conditions.The excellent catalytic performance of xV/g-C3N4 was due to the integration of vanadium species with high catalytic activity and the g-C3N4support in their interaction with the benzene substrate.

Electrical Properties of Ultra Thin Nitride/Oxynitride Stack Dielectrics pMOS Capacitor with Refractory Metal Gate

Electrical properties of high quality ultra thin nitride/oxynitride(N/O)stack dielectrics pMOS capacitor with refractory metal gate electrode are investigated,and ultra thin (<2 nm) N/O stack gate dielectrics with significant low leakage current and high resistance to boron penetration are fabricated.Experiment results show that the stack gate dielectric of nitride/oxynitride combined with improved sputtered tungsten/titanium nitride (W/TiN) gate electrode is one of the candidates for deep sub-micron metal gate CMOS devices.

A High Performance Sub-100nm Nitride/Oxynitride Stack Gate Dielectric CMOS Device with Refractory W/TiN Metal Gates

By complementing the equivalent oxide thickness （EOT） of a 1.7nm nitride/oxynitride （N/O） stack gate dielectric （EOT- 1.7nm） with a W/TiN metal gate electrode,metal gate CMOS devices with sub-100nm gate length are fabricated in China for the first time. The key technologies adopted to restrain SCE and to improve drive ability include a 1.7nm N/O stack gate dielectric, non-CMP planarization technology, a T-type refractory W/TiN metal stack gate electrode, and a novel super steep retrograde channel doping using heavy ion implantation and a double sidewall scheme. Using these optimized key technologies, high performance 95nm metal gate CMOS devices with excellent SCE and good driving ability are fabricated. Under power supply voltages of VDS ± 1.5V and VGS± 1.8V,drive currents of 679μA/μm for nMOS and - 327μA/μm for pMOS are obtained. A subthreshold slope of 84.46mV/dec, DIBL of 34.76mV/V, and Vth of 0.26V for nMOS, and a subthreshold slope of 107.4mV/dec,DIBL of 54.46mV/V, and Vth of 0.27V for pMOS are achieved. These results show that the combined technology has indeed thoroughly eliminated the boron penetration phenomenon and polysilicon depletion effect ,effectively reduced gate tunneling leakage, and improved device reliability.