纳米板钛矿基二氧化钛中的晶格畸变

借助精确的Ｘ射线衍射测量，结合独立衍射峰对不同晶粒度纳米板钛矿基二氧化钛样品中板钛矿和金红石相的微结构参量进行了较细致的研究，给出了标明物相、晶面指数（ｈｋｌ）和晶面间距ｄｈｋｌ值详细分析结果的系列ＸＲＤ谱，并得到了晶面间距、晶格常数、轴比、晶胞体积等参数数值及其相对常规粗晶的变化情况，从而初步揭示出其晶粒微结构的尺寸效应。首次发现。

纳米板钛矿基TiO_2的晶粒尺寸效应

借助精确的 X射线衍射测量 ,结合独立衍射峰对不同晶粒度纳米板钛矿基 Ti O2 样品中板钛矿和金红石相的微结构参量进行了较细致的研究 ,给出了标征物相、晶面指数 (hk1)和晶面间距 dhkl值 ,详细分析结果的系列 XRD谱 ,并得到晶面间距、晶格常数、轴比、晶胞体积等参数数值及其相对常规粗晶的变化情况 ,从而初步揭示出其晶粒微结构的尺寸效应 .作者首次发现 ,纳米板钛矿基 Ti O2 样品中板钛矿和金红石相晶粒均存在着非单调的各向异性晶格畸变 .

Single-atom modified graphene cocatalyst for enhanced photocatalytic CO_(2) reduction on halide perovskite

Metal halide perovskite(MHP)has become one of the most promising materials for photocatalytic CO_(2) reduction owing to the wide light absorption range,negative conduction band position and high reduction ability.However,photoreduction of CO_(2) by MHP remains a challenge because of the slow charge separation and transfer.Herein,a cobalt single-atom modified nitrogen-doped graphene(Co-NG)cocatalyst is prepared for enhanced photocatalytic CO_(2) reduction of bismuth-based MHP Cs_(3)Bi_(2)Br_(9).The optimal Cs_(3)Bi_(2)Br_(9)/Co-NG composite exhibits the CO production rate of 123.16μmol g^(-1)h^(-1),which is 17.3 times higher than that of Cs_(3)Bi_(2)Br_(9).Moreover,the Cs_(3)Bi_(2)Br_(9)/Co-NG composite photocatalyst exhibits nearly 100% CO selectivity as well as impressive long-term stability.Charge carrier dynamic characterizations such as Kelvin probe force microscopy(KPFM),single-particle PL microscope and transient absorption(TA)spectroscopy demonstrate the vital role of Co-NG cocatalyst in accelerating the transfer and separation of photogenerated charges and improving photocatalytic performance.The reaction mechanism has been demonstrated by in situ diffuse reflectance infrared Fourier-transform spectroscopy measurement.In addition,in situ X-ray photoelectron spectroscopy test and theoretical calculation reveal the reaction reactive sites and reaction energy barriers,demonstrating that the introduction of Co-NG promotes the formation of ^(*)COOH intermediate,providing sufficient evidence for the highly selective generation of CO.This work provides an effective single-atom-based cocatalyst modification strategy for photocatalytic CO_(2) reduction and is expected to shed light on other photocatalytic applications.

Behaviors of vanadium and chromium in coal-based direct reduction of high-chromium vanadium-bearing titanomagnetite concentrates followed by magnetic separation

The reduction behaviors of FeO·V2O3 and FeO·Cr2O3 during coal-based direct reduction have a decisive impact on the efficient utilization of high-chromium vanadium-bearing titanomagnetite concentrates. The effects of molar ratio of C to Fe n(C)/n(Fe) and temperature on the behaviors of vanadium and chromium during direct reduction and magnetic separation were investigated. The reduced samples were characterized by X-ray diffraction(XRD), scanning election microscopy(SEM) and energy dispersive spectrometry(EDS) techniques. Experimental results indicate that the recoveries of vanadium and chromium rapidly increase from 10.0% and 9.6% to 45.3% and 74.3%, respectively, as the n(C)/n(Fe) increases from 0.8 to 1.4. At n(C)/n(Fe) of 0.8, the recoveries of vanadium and chromium are always lower than 10.0% in the whole temperature range of 1100-1250 °C. However, at n(C)/n(Fe) of 1.2, the recoveries of vanadium and chromium considerably increase from 17.8% and 33.8% to 42.4% and 76.0%, respectively, as the temperature increases from 1100 °C to 1250 °C. At n(C)/n(Fe) lower than 0.8, most of the FeO·V2O3 and FeO·Cr2O3 are not reduced to carbides because of the lack of carbonaceous reductants, and the temperature has little effect on the reduction behaviors of FeO·V2O3 and FeO·Cr2O3, resulting in very low recoveries of vanadium and chromium during magnetic separation. However, at higher n(C)/n(Fe), the reduction rates of FeO·V2O3 and FeO·Cr2O3 increase significatly because of the excess amount of carbonaceous reductants. Moreover, higher temperatures largely induce the reduction of FeO·V2O3 and FeO·Cr2O3 to carbides. The newly formed carbides are then dissolved in the γ(FCC) phase, and recovered accompanied with the metallic iron during magnetic separation.

Post treatment preparation of hybrid metal halide perovskite nanocrystal-embedded polymethylmethacrylate blends with enhanced stablity

Hybrid organic-inorganic perovskites have been the subject of recent intense interest due to advances in photovoltaic and other optoelectronic applications. However, their poor stability limits commercial market application We enhance water stability by post treatment preparation of hybrid metal halide perovskite nanocrystal-embedded polymethylmethacrylate （PM- MA） blend films. Through blending process without any cleaning of nanocrystals, crystalline hybrid organic-inorganic perovs-kite nanocrystals were incorporated into PMMA matrix with well-dispersion Passivation of PMMA on the surface of the per-ovskite nanocrystals results in decreased traps and a long photoluminescence （PL） lifetime despite the bromine vacancies in the crystal lattice. Moreover, such color purity and inherent high transmittance for fluorescence emission of perovskite nanocrystals will endow the films with promising potentials in diverse practice photonic applications.

Effect of reducing agents on reducing atmosphere in coal-based direct reduction of beach titanomagnetite

Beach titanomagnetite(TTM)provides a cheap alternative source of Fe and Ti,but this ore is difficult to process to make suitable concentrates for the blast furnace.Recently studies showed that it is feasible to separate Fe and Ti by coal-based direct reduction.In this study,beach TTM was selected as the research object,the effects of reducing agents on reducing atmosphere in coal-based direct reduction of beach TTM were analyzed,and the role of volatiles was also studied.The results showed that when bitumite and coke were used as reducing agents of TTM,the CO produced from volatiles was involved in the reduction reaction,and the generated CO_(2) provided the raw material for the reaction of TTM.The reduction effect of bitumite was better than that of coke.The reason is that bitumite+TTM had a higher gas generation rate and produced a higher CO partial pressure,while coke+TTM had a lower gas generation rate and produced a lower CO partial pressure.When graphite was used as a reducing agent,there was a solid-solid reaction in the early stage in the reaction.With the continuous accumulation of CO_(2),the Boudouad reaction started and accelerated.Graphite+TTM also produced a higher CO partial pressure.

Influence of rutile(TiO_2) content on wear and microhardness characteristics of aluminium-based hybrid composites synthesized by powder metallurgy

The effect of rutile（TiO_2） content on the wear and microhardness properties of aluminium（Al）-based hybrid composites was explored. The proposed content of TiO_2（0, 4%, 8%, 12%, mass fraction） was blended to Al-15% SiC composites through powder metallurgy（P/M） process. Wear test was conducted using pin-on-disc apparatus under dry sliding conditions. Fabricated preforms were characterized using X-ray diffractometer（XRD）, scanning electron microscope（SEM） and energy-dispersive X-ray spectrometer（EDS）. Optical micrographs of the composite preforms display uniform distribution of TiO_2 throughout the matrix. Quantitative results indicate that wear resistance and microhardness increase with the increase of TiO_2 content. SEM images unveil that high wear resistance is attributed to high dislocation density of deformed planes and high hardness of TiO_2. SEM images of wear debris display gradual reduction in mean size of debris when TiO_2 content increases. EDS spectra confirm the presence of oxide layer which obviously reduces the effective area of contact between the sliding surfaces thereby lowers the wear loss of composites. The observation concludes that delamination and adhesive wear are the predominant mechanisms.

Direct decomposition of nitric oxide in low temperature over iron-based perovskite-type catalyst modified by Ru

Iron-based perovskite-type compounds modified by Ru were prepared through sol-gel process to study its catalytic activity of NOx direct decomposition at low temperature and evaluate the conversion of NO under the experimental conditions. The catalytic activity of La 0.9Ce 0.1Fe 0.8-nCo 0.2RunO3 （n=0.01,0.03,0.05,0.07,0.09）series for the NO, NO-CO two components, CO-HC-NO three components were also analyzed. The catalytic investigation evidenced that the presence of Ru is necessary for making highly activity in decomposition of nitric oxide even at low temperature（400 ℃）and La 0.9Ce 0.9Fe 0.75Co 0.2Ru 0.05O3 （n=0.05） has better activity in all the samples, the conversion of it is 58.5%. With the reducing gas（CO,C3H6）added into the gas, the catalyst displayed very high activity in decomposition of NO and the conversion of it is 80% and 92.5% separately.

Aromatic bromination with hydrogen production on organic‐inorganic hybrid perovskite‐based photocatalysts under visible light irradiation

Aromatic bromides are important chemicals in nature and chemical industries.However,their tra‐ditional synthesis routes suffer from low atomic economy and pollutant formation.Herein,we show that organic-inorganic hybrid perovskite methylammonium lead bromide(MAPbBr_(3))nanocrystals stabilized in aqueous HBr solution can achieve simultaneous aromatic bromination and hydrogen evolution using HBr as the bromine source under visible light irradiation.By hybridizing MAPbBr_(3) with Pt/Ta_(2)O_(5) and poly(3,4‐ethylenedioxythiophene)polystyrene sulfonate as electron‐and hole‐transporting motifs,aromatic bromides were achieved from aromatic compounds with high yield(up to 99%)and selectivity(up to 99%)with the addition of N,N‐dimethylformamide or its analogs.The mechanistic studies revealed that the bromination proceeds via an electrophilic attack pathway and that HOBr may be the key intermediate in the bromination reaction.

Comparison of wear behaviour of LM13 Al−Si alloy based composites reinforced with synthetic(B_(4)C)and natural(ilmenite)ceramic particles

Dry sliding wear behaviour of stir-cast aluminium matrix composites(AMCs)containing LM13 alloy as matrix and ceramic particles as reinforcement was investigated.Two different ceramic particle reinforcements were used separately:synthetic ceramic particles(B_(4)C),and natural ceramic particles(ilmenite).Optical micrographs showed uniform dispersion of reinforced particles in the matrix material.Reinforced particles refined the grain size of eutectic silicon and changed its morphology to globular type.B_(4)C reinforced composites(BRCs)showed maximum improvement in hardness of AMCs.Ilmenite reinforced composites(IRCs)showed maximum reduction in coefficient of friction values due to strong matrix−reinforcement interfacial bonding caused by the formation of interfacial compounds.Dry sliding wear behaviour of composites was significantly improved as compared to base alloy.The low density and high hardness of B_(4)C particles resulted in high dislocation density around filler particles in BRCs.On the other hand,the low thermal conductivity of ilmenite particles resulted in early oxidation and formation of a tribo-layer on surface of IRCs.So,both types of reinforcements led to the improvement in wear properties of AMCs,though the mechanisms involved were very different.Thus,the low-cost ilmenite particles can be used as alternative fillers to the high-cost B_(4)C particles for processing of wear resistant composites.

Improvement in Performance of Carbon-based Perovskite Solar Cells through Interface Modification with CTAC

Carbon-based perovskite solar cells have attracted much attention,due to their low cost,simple preparation process and high chemical stability.However,the devices exhibit low photoelectric conversion efficiency,owing to the presence of defects and interface impedance between the perovskite active layer and the contact interface.In order to minimize the interfacial defects and improve the charge transfer performance between the perovskite layer and the contact interface,cetyltrimethylammonium chloride(CTAC)was introduced into the lower interface of HTL-free carbon-based perovskite solar cells,because CTAC can be used as interface modification material to passivate the buried interface of perovskite and promote grain growth.It was found that CTAC can not only passivate the interface defects of perovskite,but also improve the crystalline quality of perovskite.As a result,the photovoltaic conversion efficiency of reaches 17.18%,which is 12.5%higher than that of the control group.After 20 days in air with 60%RH humidity,the cell can still maintain more than 90%of the initial efficiency,which provides a new strategy for interfacial passivation of perovskite solar cells.

Organic-inorganic hybrid Sn-based perovskite photodetectors with high external quantum efficiencies and wide spectral responses from 300 to 1000 nm

Organic-inorganic hybrid perovskites are ideal materials for photodetection owing to their high charge carrier mobility, long charge carrier diffusion length, low dark current density and sharp absorption edge. However, a relatively small band gap(1.6 e V) limits their photonharvesting efficiency in the near-infrared region. In the present work, we demonstrate a hybrid methylamine iodide and Pb-Sn binary perovskite as the light absorption layer in photodetectors. Experimentally, the wavelength of photoresponse onset for the photodetectors can be extended to as great as 1,000 nm when the Sn content of the hybrid perovskite is increased to 30 mol%. In addition, the photodetectors exhibit a photoresponsivity of 0.39 A W^-1, a specific detectivity of 7×10^12 Jones, a fast photoresponse with rise and decay time constants and an external quantum efficiency greater than 50% in the wavelength range of350–900 nm, with a maximum value of about 80% at 550 nm.

An in-situ defect passivation through a green anti-solvent approach for high-efficiency and stable perovskite solar cells

Surface and grain boundary defects in halide perovskite solar cells are highly detrimental,reducing efficiencies and stabilities.Widespread halide anion and organic cation defects usually aggravate ion diffusion and material degradation on the surfaces and at the grain boundaries of perovskite films.In this study,we employ an in-situ green method utilizing nontoxic cetyltrimethylammonium chloride(CTAC)and isopropanol(IPA)as anti-solvents to effectively passivate both surface and grain boundary defects in hybrid perovskites.Anion vacancies can be readily passivated by the chloride group due to its high electronegativity,and cation defects can be synchronously passivated by the more stable cetyltrimethylammonium group.The results show that the charge trap density was significantly reduced,while the carrier recombination lifetime was markedly extended.As a result,the power conversion efficiency of the cell can reach 23.4%with this in-situ green method.In addition,the device retains 85%of its original power conversion efficiency after 600 h of operation under illumination,showing that the stability of perovskite solar cells is improved with this in-situ passivation strategy.This work may provide a green and effective route to improve both the stability and efficiency of perovskite solar cells.

Stable tin perovskite solar cells developed via additive engineering

Tin perovskite solar cells(TPSCs)are promising for lead-free perovskite solar cells(PSCs)and have led to extensive research;however,the poor crystallinity and chemical stability of tin perovskites are two issues that prevent stable TPSCs.In this study,we outline a new process that addresses these issues by using tin(II)acetate(Sn(Ac)2)in place of the conventional SnF2 precursor additive.Compared with SnF2,Sn(Ac)2 improves the crystallinity and stability of tin perovskite with fewer defects and better charge extraction.Using this process,we developed a device that has a higher external quantum efficiency for charge extraction compared with the control devices and a power conversion efficiency of 9.93%,which maintained more than 90%of its initial efficiency after 1000 h operation at the maximum power point under standard AM 1.5G solar illumination.

Fullerenes and derivatives as electron transport materials in perovskite solar cells

In this study,two fullerenes(C60,C70)and their methano-substitutions(PC61BM,PC71BM),as electron transport materials(ETMs)in perovskite solar cells(Pero-SCs),were systematically studied.As being used as ETMs,methanofullerenes,though with lower electron mobility compared to the counterpart pristine fullerenes,lead to higher power conversion efficiencies(PCEs)of Pero-SCs.The difference is likely caused by the fill-out vacancies and smoother morphology of the interfaces between ETM and perovskite layers,as they were prepared by different methods.In addition,compared to C60 and PC61BM,C70 and PC71BM showed priority in terms of short-circuit current density,which should be attributed to fast free charge extraction abilities.

A stable lead halide perovskite nanocrystals protected by PMMA

To enhance the stability in humidity is very crucial to hybrid organic-inorganic lead halide perovskites in a broad range of applications. This report describes a coating stratergy of perovskite nanocrystals via poly- methylmethacrylate-introdnced ligand-assisted reprecipita- tion, using the interactions between the Pb cations on the surface of perovskite nanocrystals and the functional ester carbonyl groups in polymethylmethacrylate framework. The hydrophobic framework shields the open metal sites of hybrid organic-inorganic lead halide perovskites from being attacked by water, effectively retarding the diffusion of water into the perovskite nanocrystals. The as-prepared films demonstrate high resistance to heat and moisture. Additionally, the in- troduction of polymethylmethacrylate into ligand-assisted reprecipitation can effectively control the bulk precipitation and promote the stability of the perovskite solution.