An efficient method for the synthesis of dialkyl chlorophosphates from trialkyl phosphites using bis(trichloromethyl)carbonate

A mild and simple method for the synthesis of dialkyl chlorophosphates is described, bis（trichloromethyl） carbonate （BTC） is used as the effective reagent for the conversion of dialkyl phosphites to their corresponding dialkyl chlorophosphates under mild conditions.

Bifunctional S-scheme g-C3N4/Bi/BiVO4 hybrid photocatalysts toward artificial carbon cycling

Although both the aerobic photocatalytic oxidation of organic pollutants into CO2 and the anaerobic photocatalytic reduction of CO2 into solar fuels have been intensively studied,few efforts have been devoted to combining these carbon-involved photocatalytic oxidation-reduction processes together,by which an artificial photocatalytic carbon cycling process can be established.The key challenge lies in the exploitation of efficient bifunctional photocatalysts,capable of triggering both aerobic oxidation and anaerobic reduction reactions.In this work,a bifunctional ternary g-C3N4/Bi/BiVO4 hybrid photocatalyst is successfully constructed,which not only demonstrates superior aerobic photocatalytic oxidation performance in degrading an organic pollutant(using the dye,Rhodamine B as a model),but also exhibits impressive photocatalytic CO2 reduction performance under anaerobic conditions.Moreover,a direct conversion of Rhodamine B to solar fuels in a one-pot anaerobic reactor can be achieved with the as-prepared ternary g-C3N4/Bi/BiVO4 hybrid photocatalyst.The excellent bifunctional photocatalytic performance of the g-C3N4/Bi/BiVO4 photocatalyst is associated with the formation of efficient S-scheme hybrid junctions,which contribute to promoting the appropriate charge dynamics,and sustaining favorable charge potentials.The formation of the S-scheme heterojunction is supported by scavenger studies and density functional theory calculations.Moreover,the in-situ formed plasmonic metallic Bi nanoparticles in the S-scheme hybrid g-C3N4/Bi/BiVO4 photocatalyst enhances vectorial interfacial electron transfer.This novel bifunctional S-scheme g-C3N4/Bi/BiVO4 hybrid photocatalyst system provides new insights for the further development of an integrated aerobic-anaerobic reaction system for photocatalytic carbon cycling.

Bi Nanoparticles Anchored in N-Doped Porous Carbon as Anode of High Energy Density Lithium Ion Battery

A novel bismuth–carbon composite, in which bismuth nanoparticles were anchored in a nitrogen-doped carbon matrix(Bi@NC), is proposed as anode for high volumetric energy density lithium ion batteries(LIBs).Bi@NC composite was synthesized via carbonization of Zn-containing zeolitic imidazolate(ZIF-8) and replacement of Zn with Bi, resulting in the N-doped carbon that was hierarchically porous and anchored with Bi nanoparticles. The matrix provides a highly electronic conductive network that facilitates the lithiation/delithiation of Bi.Additionally, it restrains aggregation of Bi nanoparticles and serves as a buffer layer to alleviate the mechanical strain of Bi nanoparticles upon Li insertion/extraction.With these contributions, Bi@NC exhibits excellent cycling stability and rate capacity compared to bare Bi nanoparticles or their simple composites with carbon. This study provides a new approach for fabricating high volumetric energy density LIBs.

Bi nanoparticles in situ encapsulated by carbon film as high-performance anode materials for Li-ion batteries

Bismuth (Bi) has indeed inspired great interests in lithium-ion batteries (LIBs) due to the high capacity,but was still limited by the low electrical conductivity and large volume variation.Herein,a composite material based on Bi nanoparticles in situ encapsulated by carbon film (Bi@CF) is prepared successfully through a facile metal–organic framework (MOF)-engaged approach.As anode materials for LIBs,the Bi@CF composites achieved high reversible capacities of 705 and 538 mAh g^(-1)at 0.2 and 0.5 A g^(-1) after200 cycles,and long cycling performance with a stable capacity of 306 mAh g^(-1)at 1.0 A g^(-1) even after 900 cycles.In situ X-ray diffraction (XRD) measurements clearly revealed the conversion between Bi and Li_(3)Bi during the alloying/dealloying process,confirming the good electrochemical reversibility of Bi@CF for Li-storage.The reaction kinetics of this Bi@CF composite was further studied by galvanostatic intermittent titration technique (GITT).This work may provide an inspiration for the elaborate design and facile preparation of alloy-type anode materials for high-performance rechargeable batteries.

Liver Nuclear Activation of Carbon Tetrachloride or Bromotrichloromethane to Trichloromethyl and Trichloromethylperoxyl Free Radicals.Their Reactions With Lipids and Proteins

The formation of·CCl3 radicals in liver nuclei was suggested by spin trapping of them with N-t-butyl-α-phenylnitrone followed by GC/MS detection of the resulting adduct. Comparison of its formation in microsomal biotransformation of CCl4 was made. In aerobic nuclear activation mixtures containing NADPH and CCl4, significant decrease in the arachidonic acid content of nuclear lipids was observed (27. 8%, compared to control), the intensity of this decrease was lower than that occurring in the corresponding microsomal incubation mixtures (29.1%). Significant decreases in arachidonic acid content of nuclear and endoplasmic reticulum lipids were also observed in animals at 6 hours of poisoning with the haloalkane. During aerobic nuclear metabolism of CCl4 or CBrCl3, cholesterol oxidation products were detected: a ketocholesterol, an epoxide like structure and 7-ketocholesterol. Nuclear protein carbonyl formation was not promoted during nuclear CCl4 biotransformation. NADPH by itself may lead to protein carbonyl formation during prolonged periods of incubation. CBrCl3 in contrast, led to decreased protein carbonyl formation. No increase in nuclear protein carbonyl formation was observed in CCl4 intoxicated animals during periods of time between 1 to 6 hours after treatment. The results indicate that during nuclear biotransformation of CCl4 or CBrCl3 reactive free radicals, PUFA degradation, reactive aldehydes and cholesterol oxidation products are formed, nearby DNA and regulatory proteins.

Bi/Bi_(3)Se_(4) nanoparticles embedded in hollow porous carbon nanorod:High rate capability material for potassium-ion batteries

Considering their superior theoretical capacity and low voltage plateau,bismuth(Bi)-based materials are being widely explored for application in potassium-ion batteries(PIBs).Unfortunately,pure Bi and Bibased compounds suffer from severe electrochemical polarization,agglomeration,and dramatic volume fluctuations.To develop an advanced bismuth-based anode material with high reactivity and durability,in this work,the pyrolysis of Bi-based metal-organic frameworks and in-situ selenization techniques have been successfully used to produce a Bi-based composite with high capacity and unique structure,in which Bi/Bi_(3)Se_(4)nanoparticles are encapsulated in carbon nanorods(Bi/Bi_(3)Se_(4)@CNR).Applied as the anode material of PIBs,the Bi/Bi_(3)Se_(4)@CNR displays fast potassium storage capability with 307.5 m A h g^(-1)at 20 A g^(-1)and durable cycle performance of 2000 cycles at 5 A g^(-1).Notably,the Bi/Bi_(3)Se_(4)@CNR also showed long cycle stability over 1600 cycles when working in a full cell system with potassium vanadate as the cathode material,which further demonstrates its promising potential in the field of PIBs.Additionally,the dual potassium storage mechanism of the Bi/Bi_(3)Se_(4)@CNR based on conversion and alloying reaction has also been revealed by in-situ X-ray diffraction.

Catalytic Effect of Cobalt and Iron Complexes Incorporating Bis(2-aldiminoethyl)amine Ligands on Ethylene Oligomerization

Complexes [MCl 2{CH 3N(CH 2CH 2N[CDS1]CR 1R 2) 2}]((3, M=Co, R 1=H, R 2=Ph ; 4, M=Fe, R 1=H, \{R 2=Ph\}; 5, M=Co, R 1=R 2=Ph) were prepared and characterized by IR spectra and elemental analysis. The combination of each of complexes 3-5 with ethylaluminoxane(EAO), respectively, was found to be moderately active for ethylene oligomerization to low carbon olefins. The activity of 113 kg oligomers·mol -1 Co·h -1 for complex 3(100 mol of EAO, 180 ℃ and 1 8 MPa ethylene) was observed with a selectivity of 93% to C 4-10 olefins, of which 96% were linear C4 10 olefins. The catalytic properties of complexes 3-5 were compared with those of analogous P,P coordinated complexes [MCl 2{CH 3N(CH 2CH 2PPh 2) 2}](1, M=Co; 2, \{M=\}Fe).

Implementation of a choline bis(trifluoromethylsulfonyl)imide aqueous electrolyte for low temperature EDLCs enabled by a cosolvent

We report a carbon/carbon capacitor based on micro/mesoporous carbon electrodes with cost-effective and eco-friendly aqueous choline bis(trifluoromethylsulfonyl)imide(Ch TFSI)electrolyte with a cosolvent enabling low-temperature operation down to-30℃.For this purpose,a Mg O-templated hierarchical carbon(MP98B)with an average mesopore diameter of 3.5 nm was prepared by pyrolysis of magnesium citrate hydrate at 900℃.To reach lower temperatures,the melting point and viscosity of the aqueous electrolyte were reduced by mixing water(W)with an organic solvent(methanol,M,or isopropanol,I)of high dielectric constant and low viscosity.5 mol kg^(-1)(5 m)Ch TFSI in an optimized volume fraction of cosolvent,M_(0.75)W_(0.25),and I_(0.75)W_(0.25),showed the highest conductivity;the higher conductivity in M_(0.75)W_(0.25)(22.8 and 3.1 m S cm^(-1) at 20 and-30℃,respectively)than in I_(0.75)W_(0.25)(8.5 and0.5 m S cm^(-1)at 20 and-30℃,respectively)is attributed to the lower viscosity of the M_(0.75)W_(0.25)solution.The electrochemical stability window(ESW)of 5 m Ch TFSI in M_(0.75)W_(0.25)and I_(0.75)W_(0.25)(1.6 V)on an MP98B electrode was determined by applying the S-method.Meanwhile,by adjusting the mass ratio of the two electrodes,a MP98B/MP98B capacitor using the 5 m electrolyte in M_(0.75)W_(0.25)could operate with a good life span up to 1.6 V while exhibiting a better charge propagation,greater specific capacitance,and higher specific energy than in I_(0.75)W_(0.25).

CNTs增强Sn-Bi基复合钎料回流焊焊点显微组织及力学性能

目的为了解决Sn-Bi焊点难以满足高密度封装结构长期服役可靠性要求的难题,研制了CNTs增强Sn-Bi基复合钎料,并分析了复合钎料对焊点组织与力学性能的影响。方法采用机械混合方式制备了不同碳纳米管(CNTs)含量(0%、0.01%、0.025%、0.1%、0.25%,质量分数)的Sn-58Bi基复合钎料,随后采用回流焊方法对Cu薄板进行搭接焊。通过SEM、EDS等技术分析了焊点内的显微组织及界面金属间化合物(Inermetallic Compound,IMC)变化,并使用拉力测试仪研究了焊点剪切强度的变化规律。结果Cu/Sn-58Bi/Cu焊点的显微组织主要为黑色树枝状富Sn相和灰白色层片状富Bi的共晶组织,界面处IMC成分为扇贝状的Cu_(6)Sn_(5)相。添加CNTs可以明显细化组织晶粒,当CNTs质量分数为0.025%时,组织细化最明显。在Sn-58Bi钎料中添加一定量的CNTs可以明显提高焊点的剪切性能,当CNTs质量分数为0.025%时,焊点剪切性能最优,其剪切强度为27.5MPa,相较于Sn-58Bi/Cu焊点,提高了43.37%。结论在一定范围内,随着CNTs含量的增加,Sn-Bi-CNTs复合钎料焊点的显微组织得到明显细化,焊点拉剪性能显著提高。

An approach to synthesis of(Z)-2-chloro-1,3-diarylpropen-1-ones by Vilsmeier reagent(bis-(trichloromethyl)carbonate/DMF)

A series of（Z）-2-chloro-1,3-diarylpropen-1-ones were unexpectedly synthesized in moderate yields by treatment of easily available 2,3-epoxy-1,3-diarylpropan-1-ones with Vilsmeier reagent,which was derived from bis（trichloromethyl） carbonate（BTC, triphosgene） and DMF.A possible mechanism was also proposed,where sequential ring-opening,halogenation and elimination reactions were involved.

MWCNT/Bi_2WO_6复合光催化剂的制备及其活性研究

采用水热合成法将多壁碳纳米管(MWCNT)和Bi_2WO_6有效复合,制备了具有高效光催化活性的MWCNT/Bi_2WO_6催化剂。利用XRD、SEM、TEM、XPS、BET和UV-Vis等技术对样品进行表征分析,以罗丹明B为目标污染物,考察了催化剂的光催化性能。结果表明,合成的样品均为斜方晶体结构,MWCNT交互附着在Bi_2WO_6片层结构的周围,两者紧密接触形成了复合物。合成的MWCNT/Bi_2WO_6样品具有较大的比表面积和较小的禁带宽度,能有效抑制光生电子和空穴的复合,增加了量子的传递效率,更容易被光照激发。当MWCNT负载量为2%(质量分数)时,催化剂表现出了最佳的催化性能,在模拟太阳光试验中,该催化剂对10 mg/L的罗丹明B溶液光降解效率高达98. 8%。

碳纳米管表面基团对Bi基催化剂在乙炔氢氯化反应中催化性能的影响

以多壁碳纳米管(MWCNTs)、羟基碳纳米管(MWCNTs-OH)、羧基碳纳米管(MWCNTsCOOH)为催化剂载体,采用等体积浸渍法制备负载型Bi基催化剂,在固定床反应器中评价催化剂在乙炔氢氯化反应中的性能。结果表明,以MWCNTs-OH为载体的Bi基催化剂催化性能最优,乙炔转化率最高52%。BET、FT-IR、XRD、XPS、EDS、TG、TEM和H_2-TPR表征表明,碳纳米管表面基团,尤其是羟基,可以提高活性组分的分散度、抑制催化剂表面积炭生成和减少Bi物种流失。

导电炭黑和热处理对Al-Bi复合材料产氢性能的影响

采用机械球磨法制备Al-Bi-CB复合材料,研究了导电炭黑和热处理对Al-Bi复合材料产氢性能的影响,用扫描电子显微镜和X射线衍射仪分析了复合材料的组织形貌和物相结构。实验结果表明,当导电炭黑含量为5%时,复合材料的产氢性能最佳。在30℃时,1 g Al-3%Bi-5%CB复合材料5 min产生865 mL氢气,最大产氢速率达到107.15 mL·s^(-1)。导电炭黑细化铝粉体颗粒、提高Al-Bi复合材料的导电性以及与水接触时导电炭黑能迅速从复合材料表面剥落是其提高Al-Bi复合材料产氢量和产氢速率的主要原因。球磨Al-Bi-CB粉体材料经热处理后,在30 min内,1 g Al-3%Bi-1%CB材料的最大产氢量从220 mL增至840 mL,热处理后嵌入Al中的Bi重新熔化与再结晶而覆盖在Al表面形成活性位点是提高复合材料产氢性能的主要原因。

Bi quantum dots implanted 2D C-doped BiOCl nanosheets: Enhanced visible light photocatalysis efficiency and reaction pathway

The simultaneous integration of heteroatom doping and surface plasmon resonance(SPR) modulation on semiconductor photocatalysts could be capable of improving visible light utilization and charge separation, achieving better solar light conversion and photocatalysis efficiency. For this purpose, we have designed a novel Bi quantum dots(QDs) implanted C-doped BiOCl photocatalyst(C/BOC/B) for NOx removal. The feasibility was firstly evaluated through density functional theory(DFT) calculations methods, which indicates that the enhanced photocatalytic performance could be expected owing to the synergistic effects of doped C heteroatoms and loaded Bi QDs. Then, the C/BOC/B was synthesized via a facile hydrothermal method and exhibited efficient and stable visible light photocatalytic NO removal. The results found that the doped C atoms can serve as electron guides to induce oriented charge transfer from Bi QDs to BiOCl, while the Bi QDs can act as light-capture and electron-donating sites. The reaction pathway and mechanism for NO conversion was unveiled by in situ Fourier-transform infrared spectroscopy combined with DFT calculation. The enhanced adsorption of reactants and intermediates could promote the overall reaction efficiency and selectivity in photocatalytic NO conversion. This work could provide a new perspective on the mechanistic understanding of the synergistic effects toward non-metal doping and SPR effects in semiconductor photocatalysts, and this presented technique could be extended for other semiconductor materials.

Photoreduction of CO_2 to methanol over Bi_2S_3/CdS photocatalyst under visible light irradiation

The Bi2S3,CdS and Bi2S3/CdS photocatalysts were prepared by direct reactions between their corresponding salt and thiourea in a hy- drothermal autoclave.The photocatalytic activities of these photocatalysts for reducing CO2 to CH3OH under visible light irradiation have been investigated.The results show that the photocatalytic activity and visible light response of Bi2S3 are higher than those of CdS.The Bi2S3 modification can enhance the photocatalytic activity and visible light response of CdS.The photocatalytic activity of Bi2S3/CdS hetero-junction photocatalyst was the highest and the highest yields of methanol was 613μmol/g when the weight proportion of Bi2S3 to CdS was 15%,which was about three times as large as that of CdS or two times of that of Bi2S3.

Bi/Bi_(2)O_(3)复合碳纳米纤维的制备及其储锂性能研究

为提高Bi负极材料的循环性能,提出了一种Bi/Bi2O3碳纳米复合纤维(Bi/Bi2O3-CNFs)的合成方法。以Bi_(2)S_(3)纳米棒为模板,采用静电纺丝技术及后续高温热处理方法成功合成了具有纵孔结构的Bi/Bi2O3(w)-CNFs。采用扫描电子显微镜(SEM)、X射线衍射(XRD)、热重分析(TGA)、透射电子显微镜(TEM)和X-射线光电子能谱(XPS)对复合材料进行了表征。讨论了不同质量分数的Bi_(2)S_(3)对复合材料结构以及电化学性能的影响。结果表明:当添加8.7%(质量分数)的Bi_(2)S_(3)时,合成的Bi/Bi2O3(8.7%)-CNFs拥有最佳的电化学储锂性能。当充放电电流密度为0.1 A/g时,Bi/Bi2O3(8.7%)-CNFs复合材料首次放电比容量可达到806 mA·h/g,并能稳定循环1000次,即使在5.0 A/g的大电流密度下,储锂容量仍有147 mA·h/g。Bi/Bi2O3(8.7%)-CNFs复合结构改善了充放电过程的动力学性能,提高了电化学性能。碳纤维及内部纵孔结构缓解了充放电过程中电极材料的体积膨胀,增强了电池的循环稳定性。

环保型含Bi低碳高硫易切削钢的开发

开发Bi易切削钢1215M(%:0.06C、0.04Si、1.25Mn、0.39S、0.17Bi)替代Pb易切削钢SUM24L。生产Bi易切削钢的流程为40t UHP EAF-40t LF(喂Bi线)-180 mm×180 mm连铸-连轧工艺。试验结果表明,Bi易切削钢1215MΦ9 mm盘条夹杂物分布均匀,Bi易切削钢1215M的切削性能优于SUM23HS含S易切削钢与SUM24L含Pb易切削钢相当。

CICC型Bi-2212超导磁体绝缘纤维预处理方法研究

选择成分均为72%γAl_(2)O_(3)+28%SiO_(2)的氧化铝纤维制品作为Bi-2212超导磁体绝缘纤维材料并进行空气热处理除碳。采用强度测试、SEM、TG-DSC等测试手段,对三种氧化铝纤维制品(宽25mm/厚0.2mm氧化铝纤维带A、宽25mm/厚0.35mm氧化铝纤维带B和200tex/3股/捻度80氧化铝纤维束C)的热失重、纤维表面形貌、纤维强度进行分析表征。结果表明,其耐温性好,热失重过程并未发现晶相转变的吸放热峰。纤维经过空气热处理后,表面浸润剂氧化挥发,纤维裸露,无缺陷暴露,直径变化不明显,强度下降不超过25%,绝缘性能提高。分析结果表明,通过600℃、2h空气热处理可以有效提高氧化铝纤维绝缘性能。

Well-defined bis(phenolate) lanthanide methoxides as efficient initiators for the polymerization of cyclic carbonate and lactide

Lanthanide methoxides supported by carbon-bridged bis(phenolate) ligands 2,2′-methylene-bis(6-tert- butyl-4-methylphenoxo) (MBMP2-) [(MBMP)Ln( μ-OMe)(THF)2]2 (Ln = Nd (1), Yb (2)) were synthesized in high yields by the protolysis reaction using (C5H5)3Ln(THF) as starting materials, and complex 1 was structurally characterized. The coordination geometry around the center metal can be best described as a distorted octahedron. Complexes 1 and 2 were shown to be efficient initiators for the ring-opening polymerization of 2,2-dimethyltrimethylene carbonate (DTC) and L-lactide. The mechanism of DTC polymerization was explored by the end group analysis of the oligomer.

基于节点碳势需求响应的电力系统双层优化调度

为实现电力系统低碳排放、助力经济提升,在建立碳势引导多元柔性负荷模型的基础上,提出一种基于节点碳势需求响应的双层优化调度策略。首先,利用比例共享原则追踪碳排放流,搭建碳排放流模型,从时空维度感知各节点的碳势变化规律。其次,将碳流分析纳入负荷侧需求响应机制中,利用节点碳势建立负荷聚合商需求响应碳排放模型,并厘清不同碳势强度下负荷聚合商调度差异,构建基于节点碳势需求响应的电力系统双层优化调度模型。模型上层为电网运营商最优经济调度,模型下层为负荷聚合商需求响应经济调度。最后,以改进IEEE 30节点系统为例,验证了所提方法的有效性。