高效利用稻壳联产木糖、多孔炭和二氧化硅

用稀酸水解半纤维素制得木糖母液,并通过正交实验得到最佳水解条件,即在130℃、稀酸质量分数2%、反应6 h的条件下,水解率可达到96.8%(以稻壳中的半纤维素为基准),去除杂质精制后木糖产率为62.8%.水解后的稻壳残渣用来制备稻壳基多孔炭和二氧化硅,其中多孔炭孔隙发达、孔径均一,可用来对木糖母液进行脱色处理,在脱色过程中对木糖的吸附损失小,达到精制木糖的目的.同时,在制备稻壳基多孔炭的过程中可同步制取高纯度二氧化硅.     

高效利用稻壳热解炭制备吸附炭与硅酸钙

报道了一种稻壳热解炭高效综合利用的方法.以稻壳热解炭为碳源和硅源,采用同步溶硅活化法分离碳和硅,采用碱溶液表面修饰法制备吸附炭,采用氧化钙沉淀法制备硅酸钙并回收碱溶液.以对孔雀石绿溶液的脱色率作为评价吸附炭性能的指标,考察制得的吸附炭的吸附性能.实验结果表明,在优化的条件下(pH=7、吸附温度30℃、吸附时间60 min),吸附炭的脱色率可达到99.9%.利用X射线衍射研究了不同钙/硅摩尔比(Ca/Si)和热处理温度下制备的硅酸钙的晶型结构.发现Ca/Si摩尔比和热处理温度对硅酸钙的晶型结构存在影响.当Ca/Si摩尔比为3,热处理温度为800℃时可以获得α_L'-Ca_2SiO_4型稻壳基硅酸钙.采用统计学方法考察了Ca/Si摩尔比、反应温度和反应时间对碱回收率的影响.其影响大小顺序为:Ca/Si摩尔比,反应温度,反应时间.当Ca/Si摩尔比为3.0时,在90℃下反应1 h后碱回收率达到100%.     

不同改性方法对酒糟生物炭理化性质及其吸附能力的影响

本文以酒糟生物炭为供试材料,比较研究了化学活化改性法(HNO₃、NaOH和H₂O₂)、有机改性法(海藻酸钠和柠檬酸)以及金属盐或金属氧化物改性法(FeCl₃和Fe₂O₃)对酒糟生物炭理化性质及其吸附性能的影响,为制备高吸附性能生物炭提供理论依据。实验结果表明:(1)不同改性方法对酒糟生物炭吸附Cd(Ⅱ)能力影响较大。吸附实验结果显示,FeCl₃改性(C₁)显著降低酒糟生物炭的吸附能力,其他改性方法均提高生物炭的吸附能力。选取三类改性方法中吸附作用最好的一种进行比较,其中Fe₂O₃改性碳(C₂)对Cd(Ⅱ)的吸附作用最强,H₂O₂改性炭(A₃)次之,柠檬酸改性炭(B₂)效果最差,三种改性生物炭与对照相比分别提高了30.45%、13.49%和10.4%。(2)生物炭...     

碱土金属Ben (n=1~3)对B12团簇结构的调控研究

基于第一性原理, 系统地研究了Be_n (n=1~3)对B₁₂团簇结构的调控. 结果表明: 团簇BeB₁₂全局极小结构为C_s对称性准平面结构, 而Be₂B₁₂和Be₃B₁₂最稳定的结构均为笼状结构, 对称性分别为C_s和C_2v. 随着Be_n (n=1~3)原子数的增加, 团簇B₁₂由准平面结构过渡到笼状结构, 且Be倾向内嵌在B₁₂笼状结构表面的B₇或B₈单元环中, 通过离子和共价作用形成稳定Be&B₇和Be&B₈单元, 从而稳定笼状结构. 自然键轨道(NBO)分析表明, 团簇C_s BeB₁₂, C_s Be₂B₁₂, C_2v Be₃B₁₂内部存在电子转移情况, Be原子2s轨道上失去电子, Be—B键主要以离子作用为主, 同时也存在共价作用. 成键分析显示C_s Be₂B₁₂和C_2v Be₃B₁₂的π键遵循球状芳香性2(n+1)² (n=1)电子计数规则, 表明该团簇具有球状芳香性. 预测了三个结构的红外和拉曼光谱, 为以后的合成实验和数据表征提供了理论基础.     

胺草磷的晶体结构

胺草磷晶体,属三斜晶系,空间群为C_i¹-P1,晶胞中含两个分子,晶体学数据为:a=8.636(1),b=10.483(2),c=10.694(2)Å;α=110.92(1)°,β=111.27(1)°,γ=98.97(1)°;V=796.2(3)ų,D_c=1.33g/cm³,F(000)=336;μ(MoK_α)=3.2cm^-1。此结构用直接法解出,最后的R因子为:R₁=O.055,R₂=0.047。胺草磷分子中的磷原子形成四个四面体向的化学键,其中P-S键含有相当高的双键成分,这意味着磷原子的3d轨函参与成键。     

粉末活性炭基复合材料制备及净化含油污水的性能和机制

针对粉末活性炭对亲水小分子有机物吸附效率低和固液分离速度慢的问题, 本研究以粉末活性炭(PAC)、腐植酸盐(HS)、聚合氯化铝(PACl)为原料, 通过融合法成功制备了粉末活性炭基复合材料PACMC (powdered activated carbon matrix composites), 将其作为含油污水的净化吸附剂. 扫描电子显微镜-X射线能量色散谱仪(SEM-EDS)和傅里叶红外光谱(FT-IR)等表征分析确认了PACMC的微观形貌和化学组成, 证实了PAC、HS和PACl是通过化学反应生成了PACMC. PACMC具有层状多孔结构和活性官能团, 有利于含油污水分子的传输扩散和化学吸附. 通过静态吸附实验研究了PACl、PAC和PACMC对含油污水中有机物的吸附性能, 结果表明: PACMC对含油污水中有机污染物的吸附能力是PAC和PACl的2~3倍(q_e=23.04 mg•g^‒1, C₀=300 mg•L^‒1); 当吸附时间达到120 min 时, PACMC上的活性位点与含油污水中有机污染物的结合已基本达到饱和(q_e=23.04 mg•g^‒1, C₀=300 mg•L^‒1). 溶液pH值对PACMC吸附去除含油污水中有机物的影响显著, pH=3时, 吸附效果最好(q_e=27.6 mg•g^‒1, C₀=300 mg•L^‒1); 伪二级动力学方程能很好地描述含油污水中有机物在PACMC上的吸附行为, 动力学拟合结果表明其吸附过程分多步进行, 化学吸附和内扩散均具有重要作用. 等温吸附数据符合Dubinin-Radushkevich模型, 证明其吸附机理为化学吸附. 因此, PACMC吸附含油污水的机理包括化学结合/螯合作用、疏水力作用和静电吸附作用.     

三元掺杂改性锂离子电池正极材料Li3V2(PO4)3

以柠檬酸为螯合剂和还原剂, NH₄VO₃为钒源,通过溶胶-凝胶法制备了锂离子电池正极材料Li₃V₂(PO₄)₃及其三元掺杂体系Li_2.85Na_0.15V_1.9Al_0.1(PO₄)_2.9F_0.1.分别采用X射线衍射(XRD)、高分辨透射电子显微镜(HRTEM)、能量损失谱(EELS)、拉曼(Raman)光谱、扫描电子显微镜(SEM)、X射线能谱(EDS)、恒流充放电、循环伏安(CV)和交流阻抗谱(EIS)等技术对材料的微观结构、颗粒形貌和电化学性能进行分析.结果表明:在残余碳包覆的基础上, Na、Al、F三元掺杂有利于稳定Li₃V₂(PO₄)₃的晶体结构,进一步减少颗粒团聚和提升材料导电特性,促进第三个锂离子的脱出和嵌入,从而显著改善Li₃V₂(PO₄)₃的实用电化学性能.未经掺杂的Li₃V₂(PO₄)₃原粉在1/9C、1C和6C倍率下的可逆比容量分别为141、119和98 mAh·g^-1,而三元掺杂改性材料在1/9C、1C、8C和14C倍率下的比容量分别为172、139、119和115 mAh·g^-1.在1C倍率下循环300圈后,掺杂体系的比容量依然高达118 mAh·g^-1,比原粉高出32.6%.值得注意的是,这种三元掺杂还使Li₃V₂(PO₄)₃的多平台放电曲线近似转变为一条斜线,显示出可能不同的储锂机制.     

宏观均相多孔电极电化学阻抗谱基础

电化学阻抗谱可用于诊断多孔电极内电荷转移反应,即界面电荷集聚和电荷传导,以及反应物质输运。本文采用复相量方法,在同态假设条件下,重新推演多孔电极阻抗谱模型,厘清传统多孔电极阻抗谱模型中的模糊性表述。(1) 定义多孔电极表征输入参数,包括电极基体电子电导率σ₁ 、电解质离子电导率σ₂、界面电荷传递电导率g_ct、单位面积界面电容C、固相扩散系数D、速度常数k、电极厚度d、特征孔深L_p 和单位体积表面积S_c;(2) 解析阻抗谱特征输出参数,包括场扩散常数K,特征频率ω₀、ω₁、ω₂、ω₃和 ω_max,它们分别相关于界面传导反应、有限场扩散、氧化还原反应、孔内扩散和最小特征孔尺寸,以及分别对应于从传导到扩散和从扩散到饱和的转折频率f_k1 和f_k2;(3) 当参数X和Z同时变化时(X = σ₁和Z = d,S_c,L_p,C,g_ct,D,k),通过阻抗谱特征参数的演变规律,分析了电荷转移反应中X和Ζ参数耦合竞争;(4)为深入分析电荷转移反应中参数X和Z的耦合竞争,引入了分叉频率f_XZ和f_ZX 。f_XZ和f_ZX所处位置可以用于表征参数X和Z影响电荷转移反应的深度和广度。当分叉频率f_XZ和f_ZX不存在时,表明电荷转移反应中参数X和Z在全频率范围内存在耦合竞争。总之,借助于特征频率和分叉频率,本文一方面研究了动力学参数和微观结构参数对多孔电极中电荷转移反应的影响,另一方面分析谱图的变化及其背后的阻抗谱特征演化规律。本文研究结果可为阻抗谱的系统仿真和辨识提供理论基础,可为多孔电极内电荷转移反应的竞争分析提供技术支撑,还可为电化学储能系统的优化设计提供诊断工具。     

离子液体辅助条件下由稻壳合成超级电容器用多孔炭

本文以稻壳为碳源,以离子液体1-丁基-3-甲基咪唑六氟磷酸盐(BMIMPF₆)为模板和辅助活化剂制备了多孔炭材料（PCs）. 多孔炭的比表面积达1438 m²·g^-1,总孔容达0.75 cm³·g^-1. 以PCs为超级电容器电极材料,6 mol·L^-1的KOH溶液为电解液组装成扣式电池,在0.05 A·g^-1的电流密度下,比电容高达256 F·g^-1;当电流密度增大至10 A·g^-1,其比电容仍保持在211 F·g^-1,展现出好的倍率性能. 所得的多孔炭电极均表现出优异的循环稳定性. 这一工作以BMIMPF₆作为模板和辅助活化剂,为合成生物质基超级电容器用多孔炭提供了一种新方法.     

邻二氯苯激发态动力学

利用飞秒分辨的激光泵浦-探测技术结合飞行时间质谱和光电子速度成像方法研究了邻二氯苯第一电子单重激发态(S₁)的超快动力学.邻二氯苯的S₁态振动基态寿命为(651 ± 10) ps,对应于S₁振动基态向三重态的系间窜越过程.邻二氯苯S₁的高振动激发9a₂18a₂对应两个衰减通道,其中寿命为(458 ± 12) fs的超快过程对应于由处于振动激发的S₁向高振动激发的基态(S₀)发生的内转换过程,而寿命为(90 ± 10) ps过程则对应由S₁态向三重态(T₁)的系间窜越过程,电离产生的光电子能谱中长寿命的谱峰可能与系间窜越过程有关. S₁态高振动态的旋轨耦合程度比低振动态的更强,导致系间窜越过程更快.     

Millimeter-wave rotational spectrum and molecular constants of diatomic gallium iodide

The gas-phase molecular spectrum of Gal has been detected in the millimeter wavelength region. The molecules are produced by vapourising a mixture of gallium and lead iodide into an evaculated cell. Analysis of the observed rotational transitions yields the following molecular parameters for ⁶⁹Ga¹²⁷I: Y₀₁ = 1706.89645(83) MHz, Y₁₁ = −5.68714(53) MHz, Y₂₁ = 6.329(43) kHz, Y₀₂ = −0.472713(60) kHz, Y₁₂ = 0.472(38) Hz, ω_e = 216.38 cm⁻¹, ω_e^x_e= 0.471 cm⁻¹, and for ⁷¹Ga¹²⁷I: y₀₁ = 1675.72004(71) MHz, Y₁₁ = −5.53277(57) MHz, Y₂₁ = 5.995(34) kHz, Y₀₂ = −0.455700(51) kHz, y₁₂ = 0.522(40) Hz, ω_e = 214.37 cm⁻¹, and ω_e^x_e = 0.458 cm⁻¹. The equilibrium internuclear distance obtained for Gal is r_e = 2.574667(12) Å.     

Effect of removing silica in rice husk for the preparation of activated carbon for supercapacitor applications

The significant influence of silica inside rice husk in the preparation and electrochemical performances of activated carbon are investigated. The removing of silica results in high mesoporous ratio and good rate capability.     

Microwave spectrum and conformation of isopropyl fluoroformate

The microwave spectrum of isopropyl fluoroformate is characterized by intense a-type R-branch transitions from one conformational species. The rotational constants of the ground state, A₀ = 4967.0(8) MHz, B₀ = 1704.69(2) MHz, C₀ = 1468.86(1) MHz and κ = −0.8651(2) are consistent with a τ₁ (O=COC) = 0°, τ₂(COCH) ˜35° structure. This structure can be viewed as a combination of the two conformational species found in ethyl fluoroformate. Two vibrational satellites having rotational constants A₀ = 4963(5) MHz, B₀ = 1694.11(7) MHz. C₀ = 1471.43(4) MHz and A₀=4998(6) MHz, B₀ = 1705.21(7) MHz, C₀ = 1471.10(4) MHz have been assigned.     

The effect of terminal chain modifications on the mesomorphic properties of 4,4'-disubstituted diphenyldiacetylenes

A variety of terminal chain modifications (Y) were made on the diacetylenes in which X=C_nH_2n+1, C₁₂H₂₅O and F, and Y=CH₂CH(Me)C₂H₅, COCH₃, C≡CC₅H₁₁, C_nF_2n+1C_nH_2n+1 and CH=CHCO₂C₃H₇. Mesomorphic properties were determined by hot stage polarizing microscopy and DSC. These were compared with those for the dialkyl analogues (X=C_mH_2m+1, Y=C_nH_2n+1) and a series of 1- and 2-olefins (Y=CH=CHC_nH_2n+1 and CH₂CH=CHC_nH_2n+1). The 1-olefin series showed wider range nematics than the dialkyl compounds, whereas the above modifications showed either narrow range nematic phases, no mesophase or higher melting temperatures. New transition temperature and enthalpy data are provided for some of the dialkyl and F-alkyl compounds previously reported, for comparisons. Preliminary birefringence data are also included along with the results of some heat and UV stability studies.     

C94 IPR isomeric set: large-scale computations of relative stabilities based on the Gibbs function

At present C₉₄ is one of the highest sets of isomeric fullerenes that has been characterized by ¹³C NMR spectra. This contribution reports quantum-chemical computations on the C₉₄ system. The complete set of 134 isolated-pentagon-rule isomers of C₉₄ is described by four semiempirical quantum-chemical methods (MNDO, AM1, PM3, and SAM1). The C₉₄ energetics is also checked with Hartree–Fock SCF calculations in the standard 4-31G basis set (HF/4-31G). The calculations point out a C₂ structure as the system ground state. As energetics itself cannot produce reliable relative stabilities at high temperatures, entropy terms are also computed and the relative-stability problem is entirely treated in terms of the Gibbs function. The lowest-energy structure remains the most populated isomer at higher temperatures. However, several other structures show significant populations at higher temperatures. The six most populated species at the AM1 computational level read: C₂, C₂, C₁, C₁, C_s, and C₂. This selected six-membered isomeric set indeed contains the four symmetries observed in the available experiment (C₂, C_s, C₂, and C₂). This incidence represents a good agreement with the experiment and can be viewed as another evidence that the supposed inter-isomeric thermodynamic equilibrium does exist in experiments.     

Molecular structure of 3-methylthiophene studied by gas electron diffraction combined with microwave spectroscopic data

The molecular structure of 3-methylthiophene has been determined by gas electron diffraction (GED) combined with microwave (MW) spectroscopic data. Ab initio calculations at the HF/3–21G* level were carried out and used as structural constraints in the data analysis. The torsional vibration of the methyl group was treated as a large-amplitude motion. The structural parameters were determined to be: r_{g(S---C2) = 1.719(2) Å}, r_{g(C2=C3) = 1.370(3) Å}, r_{g(C3---C6) = 1.497(6) Å}, r_{g(C2---H) = 1.101(5) Å}, CSC = 91.6(2)°, SC₂C₃ = 113.3(5)°, SC₅C₄ = 111.3(3)°, C₂C₃C₆ = 123.2(11)° and C₃C₆H = 112(2)°. The values of r(S---C₂) - r(S=C₅) and r(C₂=C₃)-r(C₄ =C₅) were fixed at the 3–21G* value of 0.002 Å. Parenthesized values are the estimated limits of error (3σ) referring to the last significant digit.     

Theoretical study on the aromaticity of the bimetallic clusters X2M2 (X=Si, Ge, M=Al, Ga)

Four neutral bimetallic clusters X₂M₂ (X=Si, Ge, M=Al, Ga) are investigated using density functional theory (DFT) and post-HF methods. The calculated results show that each of four X₂M₂ species has two energetically close stable isomers with rhombic structure (D_2h symmetry) and trapezoidal structure (C_2v symmetry) respectively. For the Ge₂Al₂ species the rhombic (D_2h) isomer is the ground state, whereas for other three species Ge₂Ga₂, Si₂Al₂, and Si₂Ga₂, the trapezoidal (C_2v) isomers are the ground states. The calculated magnetic susceptibility anisotropy (χ_anis) and nucleus-independent chemical shift (NICS) indicate that a strong diatropic ring current exists in the two heterocyclic planar isomers, suggesting they are highly aromatic. A detailed molecular orbital analysis further reveals that both heterocyclic isomers possess multiple aromaticity derived from one delocalized π MOs and two delocalized σ MOs.     

Structures and conformations of trifluoromethanesulfonic anhydride, (CF3SO2)2O, and bis(trifluoromethylsulfonyl)difluoromethane, (CF3SO2)2CF2

The geometric structures and conformational properties of trifluoromethanesulfonic anhydride, (CF₃SO₂)₂O, and bis(trifluoromethylsulfonyl)difluoromethane, (CF₃SO₂)₂CF₂ have been studied by gas electron diffraction (GED) and ab initio calculations (HF/3–21G*). The calculations predict for both systems two stable conformers with C₂ symmetry and one with C₁ symmetry. In both compounds structures with C₂ symmetry and dihedral angles SOSC ≈ 100° ((CF₃SO₂)₂O) and SCSC ≈ 150° ((CF₃SO₂)₂CF₂) are lowest in energy. According to the GED analyses the dominant conformer of (CF₃SO₂)₂O possesses C₂ symmetry with SOSC dihedral angles of 99.1(14)°. The presence of up to 30% of the two other conformers cannot be excluded; for (CF₃SO₂)₂CF₂ only one conformer with C₂ symmetry and SCSC dihedral angles of 143(2)° is observed. A complete set of geometric parameters is given.     

Structures and conformations of trifluoromethanesulfonic anhydride, (CF3SO2)2O, and bis(trifluoromethylsulfonyl)difluoromethane, (CF3SO2)2CF2

The geometric structures and conformational properties of trifluoromethanesulfonic anhydride, (CF₃SO₂)₂O, and bis(trifluoromethylsulfonyl)difluoromethane, (CF₃SO₂)₂CF₂ have been studied by gas electron diffraction (GED) and ab initio calculations (HF/3–21G*). The calculations predict for both systems two stable conformers with C₂ symmetry and one with C₁ symmetry. In both compounds structures with C₂ symmetry and dihedral angles SOSC ≈ 100° ((CF₃SO₂)₂O) and SCSC≈ 150° ((CF₃SO₂)₂CF₂ are lowest in energy. According to the GED analyses the dominant conformer of (CF₃SO₂)₂O₂ possesses C₂ symmetry with SOSC dihedral angles of 99.1(14)°. The presence of up to 30% of the two other conformers cannot be excluded; for (CF₃SO₂)₂CF₂ only one conformer with C₂ symmetry and SCSC dihedral angles of 143(2)° is observed. A complete set of geometric parameters is given.     

Pyramidane and isoelectronic pyramidal cations

Ab initio STO-3G, 4-31G and semi-empirical MINDO/3 calculations were performed on a series of C₄H₄X compounds to analyze the possibility of existence of their nonclassical C_4V pyramidal isomeric forms. It was shown that with the four-electron group X (C, N⁺, P⁺, O²⁺, S²⁺) in an apex, C_4V pyramidal structures are indeed stable, i.e., conform to local minima on the corresponding potential energy surfaces. Relative energies, molecular geometries and charge density distribution for various isomeric forms of the C₄H₄X compounds are presented. The theoretically derived strategies for an experimental trapping of the pyramidane 1, X = C and the C_4V pyramidal thiophene dication 1, X = S²⁺ are discussed.