Coordination chemistry of P, O-bidentate phosphinophenolates with Ga3+ and In3+

Novel complexes of Ga3+ and In3+ were synthesized with two hetero donor phosphinophenolate ligands (PO-, ortho-phenoxydiphenylphosphine; MePO-, 5-methyl-2-phenoxydiphenylphosphine). RPO-(R=H, Me) binds in a bidentate fashion through both the hard O and the soft P donor atoms to In3+, whereas, it only binds Ga3+ through the O donor. Electrochemical synthesis proved to be a practical synthetic approach to In2(PO)3Cl3, In(PO)3 and In(MePO)3. [In(MePO)(H2O)Cl2]2 and Ga(HPO)Cl3 were synthesized from MCl3(M=In and Ga, respectively). Both dimetallic indium complexes, [In(MePO)(H2O)Cl2]2 and In2(PO)3Cl3, incorporate phenolate oxygen atoms bridging the two metal ions. Each pair of In atoms are in a distorted octahedral geometry in each complex, with the former complex having a coordination sphere of PO3Cl2 for both indium metal ions and the latter showing a coordination sphere of PO3Cl2 for one indium and P2O3Cl for the other. Ga(HPO)Cl3 is a zwitterionic complex, with Ga having a OCl3 coordination core. All these complexes were fully characterized by a variety of techniques including X-ray crystallography.     

常压水热法合成玉米棒状In_2O_3及其性能研究

以In(NO_3)_3·4.5H_2O和(NH_2)_2CO为原料,采用常压水热法于95℃反应22 h制得氧化铟(In_2O_3)前驱物氢氧化铟,于600℃煅烧2 h合成了In_2O_3粉体,其结构、形貌及性能经紫外-可见(UV-Vis)光谱、X-射线衍射(XRD)、拉曼光谱和扫描电镜(SEM)表征。以甲基橙为目标降解物,研究了In_2O_3粉体的光催化活性。结果表明:In_2O_3粉体为体心立方晶系方铁锰矿结构和亚稳相刚玉六方结构的混合体,In_2O_3的UV-Vis谱图中出现了明显的蓝移。当In(NO_3)_3·4.5H_2O和(NH_2)_2CO物质的量比为1∶7时,In_2O_3粉体中出现了玉米棒状结构,棒状体长度约为500 nm,直径约150 nm;该棒状结构的In_2O_3对甲基橙有较好的光催化活性,在紫外光照射6.5 h后甲基橙的降解率为69.7%。     

High performance solution-processed indium oxide thin-film transistors

In2O3 thin-film transistors (TFTs) were fabricated on various dielectrics [SiO2, self-assembled nanodielectrics (SANDs)] by spin-coating In2O3 film precursor solutions consisting of ethanolamine (EAA) and InCl3 in methoxyethanol. Optimized film microstructures are characterized by the high-mobility In2O3 00 L orientation and are obtained only within a well-defined range of base: In3+ molar ratios. Electron mobilities as high as approximately 44 cm2 V(-1) s(-1) are measured for n+-Si/SAND/In2O3/Au devices using an EAA/In3+ molar ratio = 10. This result combined with Ion/Ioff ratios of approximately 10(6) and <5 V operating voltages is encouraging for high-speed applications.In2O3 thin-film transistors (TFTs) were fabricated on various dielectrics [SiO2, self-assembled nanodielectrics (SANDs)] by spin-coating In2O3 film precursor solutions consisting of ethanolamine (EAA) and InCl3 in methoxyethanol. Optimized film microstructures are characterized by the high-mobility In2O3 00 L orientation and are obtained only within a well-defined range of base: In3+ molar ratios. Electron mobilities as high as ~44 cm2 V(-1) s(-1) are measured for n+-Si/SAND/In2O3/Au devices using an EAA/In3+ molar ratio = 10. This result combined with Ion/Ioff ratios of approximately 10(6) and <5 V operating voltages is encouraging for high-speed applications.     

空心球形In2O3/ZrO2-TiO2纳米复合材料多模式光催化

本文以聚苯乙烯(PS)胶球为模板,通过一步水浴法结合煅烧后处理制备了不同比例的In_2O_3/ZrO_2-TiO_2空心球状复合材料(简写为In_2O_3/ZrO_2-TiO_2-H)。通过X-射线衍射、扫描电镜、X-射线光电子能谱、紫外-可见漫反射吸收光谱和氮气吸附-脱附等测试手段对该系列复合材料的结构、组成和形貌进行了表征。结果表明,In_2O_3/ZrO_2-TiO_2复合材料经PS模板处理后呈现空心球状结构,球壁由纳米粒子堆积而成。将In_2O_3与ZrO_2-TiO_2复合后其光吸收性能呈现了一定的红移现象,且In_2O_3/ZrO_2-TiO_2-H(1∶4)的比表面积较大(66.92m~2·g~(-1))。同时,为了考察该复合材料的光催化性能,在多模式光催化条件下对甲基橙的降解情况进行了研究。结果表明,In_2O_3/ZrO_2-TiO_2-H(1∶4)表现出较好的光催化性能,其光催化活性高于P25、ZrO_2、In_2O_3/ZrO_2-TiO_2及其他体积比的In_2O_3/ZrO_2-TiO_2-H。     

In2O3/CdO复合材料的制备及气敏特性

采用水热合成方法制备了花状In2O3纳米材料.利用X射线衍射(XRD)、扫描电镜(SEM)、能量色散X射线光谱(EDX)及透射电镜(TEM)对材料的结晶学特性及微结构进行了表征.制备的In2O3材料呈现花状,是由粒径约20nm的椭球状小颗粒构成的分级结构材料.将制备的In2O3与纳米CdO以摩尔比1:1混合后,发现制成的In2O3/CdO复合材料经热处理后呈现葡萄状多孔结构.测试In2O3/CdO复合材料制作的气敏元件处于最佳工作温度(410°C)时,对0.05×10-6(体积分数,φ)的甲醛气体表现出较高的灵敏度.对比测试发现,In2O3/CdO复合材料制作的气敏元件对不同浓度甲醛的灵敏度明显优于纯花状In2O3纳米材料.同时In2O3/CdO复合材料制作的气敏元件在乙醇、甲苯、丙酮、甲醇以及氨气等干扰气体中具有对甲醛良好的选择性.讨论了In2O3/CdO复合材料气敏元件的敏感机理.     

Aerosol assisted chemical vapor deposition of In2O3 films from Me3In and donor functionalized alcohols

The reaction of Me3In and ROH (R = CH2CH2NMe2, CH(CH3)CH2NMe2, C(CH3)2CH2OMe, CH2CH2OMe) in toluene under aerosol assisted chemical vapor deposition (AACVD) conditions leads to the production of indium oxide thin films on glass. The indium oxide films were deposited at 550 degrees C and analyzed by scanning electron microscopy (SEM), X-ray powder diffraction, wavelength dispersive analysis of X-rays (WDX), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. This CVD technique offers a rapid, convenient route to In2O3, which presumably involves the in situ formation of dimethylindium alkoxides, of the type [Me2InOR]2. In order to identify compounds present in the aerosol mist, the solution-phase reaction between Me3In and ROH (R = CH2CH2NMe2, C(CH3)2CH2OMe, CH(CH3)CH2NMe2, CH(CH2NMe2)2) at room temperature in toluene was carried out. Dimeric indium alkoxides, of the type [Me2In(OR)]2, were isolated, and their structures were determined by X-ray crystallography.     

Sensitized emission from lanthanide-doped nanoparticles embedded in a semiconductor sol-gel thin film.

In(2)O(3) sol-gel thin films made with LaF(3):Ln(3+) (Ln=Er, Nd, and Eu) nanoparticles were prepared and showed sensitized emission of the lanthanide ions after In(2)O(3) matrix excitation. The excitation spectra showed an In(2)O(3) absorption band in addition to the excitation peaks of the lanthanide ions, clearly demonstrating that there is energy transfer from the In(2)O(3) matrix to Ln(3+) (Er(3+), Nd(3+), and Eu(3+)). Similarly, HfO(2) and ZrO(2) sol-gel thin films made with LaF(3):Ln(3+) nanoparticles also showed energy transfer from the semiconductor matrix to the lanthanide ions.     

溶剂热法合成In2S3/CuSe核壳结构粉体

本文以氯化铜、氯化铟、硫脲、亚硒酸以及硒粉为原料,乙二醇及乙二胺为溶剂,采用常压溶剂热法制备了硫化铟为核硒化铜为壳(In2S3/CuSe)的核壳结构复合粉体。主要探讨了反应温度、不同反应原料以及不同表面活性剂对产物物相以及形貌的影响。通过采用X射线衍射(XRD)、扫描电镜(SEM)对产物的物相、形貌以及组成进行了表征。实验结果表明:常压溶剂热条件下可以制备得In2S3/CuSe复合粉体,其最佳反应工艺参数是:于160℃下合成In2S3粉体为核,于100℃下合成包裹在In2S3表面的CuSe粉体从而获得In2S3/CuSe核壳结构复合粉。在该工艺参数下合成产物的形貌主要由圆球状颗粒组成,粉体的粒径分布在1~2μm。此外,本文也通过添加不同种类表面活性剂对产物的形貌进行了控制。     

Selective functionalization of In2O3 nanowire mat devices for biosensing applications

A strategy to covalently attach biological molecules to the electrochemically active surface of indium oxide nanowire (In2O3 NW) mat devices is presented. A self-assembled monolayer (SAM) of 4-(1,4-dihydroxybenzene)butyl phosphonic acid (HQ-PA) was generated on an indium tin oxide (ITO)-coated glass and In2O3 NWs surface. The chemical steps required for surface derivatization were optimized on an ITO surface prior to modifying the In2O3 NWs. The hydroquinone group contained in the HQ-PA SAM was electrochemically oxidized to quinone (Q-PA) at +330 mV. The monolayer of Q-PA was allowed to react with a thiol-terminated DNA. The DNA was paired to its complementary strand tagged with a fluorescence dye. Attachment of DNA was verified using fluorescence microscopy. A device was subsequently prepared on a SiO2-supported mat of In2O3 NWs by depositing gold electrodes on the mat surface. The reaction strategy optimized on ITO was applied to this In2O3 NW-based device. Arrays of In2O3 NWs on a single substrate were electrochemically activated in a selective manner to Q-PA. Activated In2O3 NWs underwent reaction with HS-DNA and gave a positive fluorescence response after pairing with the dye-DNA. The unactivated In2O3 NWs gave no response, thus demonstrating selective functionalization of an In2O3 NW array. This can be considered a key step for the future fabrication of large-scale, inexpensive, nanoscale biosensors.     

Organoiron compounds derived from the indium 'carbene analogues', [In(N(Ar)C(Me))2CH] (Ar = dipp = 2,6-iPr2C6H3; = Mes = 2,4,6-Me3C6H2)

Oxidative insertion of the In(I) 'carbene analogues', [In{N(Dipp)C(Me))2CH] (Ar = Dipp = 2,6-iPr2C6H3; Ar = Mes = 2,4,6-Me3C6H2) into the Fe-I bond of [CpFe(CO)2I] occurred cleanly and under mild conditions to yield the In(III) compounds [CH((CH3)2CN-2,6-iPr2C6H3)2In(I)FeCp(CO)2] and [CH( (CH3)2CN-2,4,6-Me3C6H3)2In(I)FeCp(CO)2], which have been fully characterised in solution and the solid state. Attempts to abstract the iodide anion from [CH( (CH3)2CN-2,6-iPr2C6H3)2In(I)FeCp(CO)2] to form cationic species containing a coordinated indium diyl were unsuccessful and resulted in a complex mixture of products from which two ionic species were isolated. Neither cation was found to contain indium by X-ray crystallographic analysis. These observations were indicative of ill-defined decomposition pathways as have been noted by previous workers. A further attempt to form a cationic iron species containing a coordinated [In(N(Dipp)C(Me) )2CH] fragment resulted in oxidation of the iron centre from Fe(II) to Fe(III), with deposition of indium metal, and the isolation of a cationic Fe(III) beta-diketiminate complex.     

An in-depth study of supported In2O3 catalysts for the selective catalytic reduction of NOx: the influence of the oxide support

The influence of the oxide support (i.e., Al2O3, Nb2O5, SiO2, and TiO2,) on the surface properties, reduction and oxidation properties, acid-base properties, and catalytic activity of supported indium oxide catalysts has been investigated by temperature-programmed reduction/oxidation, thermogravimetry coupled to differential scanning calorimetry, ammonia and sulfur dioxide adsorption calorimetry, and reduction of NOx by ethene in highly oxygen-rich atmosphere. Two series of In2O3-containing catalysts at low (approximately 3 wt %) and at theoretical geometric monolayer (from 20 to 40 wt %) In2O3 content were prepared and their properties were compared with unsupported In2O3 material. Supports able to disperse the In2O3 aggregates with high In stabilization gave rise to active catalytic systems. Among the studied oxide supports, Al2O3 and, to a lower extent, TiO2 were found to be the best supports for obtaining active de-NOx catalysts.     

HO3+ 杂Ge-In-Sb-S玻璃陶瓷光谱特性

采用熔融淬冷法和热处理工艺制备了系列掺Ho3+的透明G eS2-In2S3-Sb2S3硫系玻璃陶瓷.测试了Ho3掺杂的基质玻璃和玻璃陶瓷样品的密度、显微硬度、红外光谱以及在900 nm激光泵浦下的近红外及中红外荧光光谱.结果表明:热处理后样品析出的晶相为In2S3和Sb2S3颗粒的混合体,晶粒尺寸限制在～100 nm以...     

One-pot synthesis of reverse type-I In2O3@In2S3 core-shell nanoparticles

A novel method to one-pot-synthesize high-quality In(2)O(3)@In(2)S(3) core-shell nanoparticles, consisting of a step of reducing In(2)O(3) core surface into a layer of active indium metal in high-temperature organic solution and a step of converting this layer to In(2)S(3) using CS(2), has been developed.     

α-Fe2O3掺杂对In2O3电导和气敏性能的影响

用化学共沉淀法制备了α Fe2O3掺杂的In2O3纳米晶微粉,研究了α Fe2O3掺杂对In2O3电导和气敏性能的影响. 结果表明, α Fe2O3和In2O3间可形成有限固溶体In2－xFexO3(0≤x≤0.40); Fe3＋对In2O3晶格中In3＋格位的部分取代,大大增强了阴阳离子间的结合力,导致材料中氧空位VO×数骤降、 自由电子的浓度变稀和电导下降. n(Fe3＋):n(In3＋)=5 :5的共沉淀粉于800 ℃下灼烧4 h所得的α Fe2O3掺杂In2O3传感器元件,对45 μmol•L－1 C2H5OH的灵敏度达54.0,为相同浓度干扰气体汽油的8倍多.     

Yb3AuGe2In3: an ordered variant of the YbAuIn structure exhibiting mixed-valent Yb behavior

Yb(3)AuGe(2)In(3) was obtained as large single crystals in high yield from reactions run in liquid indium. Single crystal X-ray diffraction data show that Yb(3)AuGe(2)In(3) is an ordered variant of YbAuIn with lattice constants, a = b = 7.3153(8) ? and c = 4.4210(5) ?, and space group P(6)2m. The parent compound YbAuIn was also studied for comparison. YbAuIn crystallizes in the ZrNiAl structure type, hexagonal, P(6)2m space group with lattice parameters a = b = 7.7127(11) ? and c = 4.0294(8) ?. In Yb(3)AuGe(2)In(3), Ge substitutes for one of the two Au positions in the ternary compound Yb(3)Au(3)In(3). The structure can be described as alternating [Ge(2)In(3)] and [Yb(3)Au] slabs that stack along the c-axis. The magnetic susceptibility data follow a modified Curie-Weiss law. The effective magnetic moment μ(eff) of 0.52 μ(B)/Yb atom was deduced from the Curie constant and Curie-Weiss constant of θ(p) = -1.5 K indicating antiferromagnetic interactions in Yb(3)AuGe(2)In(3). X-ray absorption near edge spectroscopy (XANES) measurements indicate intermediate valency for Yb in both compounds. The metallic nature of both compounds was confirmed by the resistivity measurements. Specific heat data for Yb(3)AuGe(2)In(3) and YbAuIn give an electronic γ term of 31 and 84 mJ/mol·K(2), respectively, suggesting that the ternary analog is a "light" heavy fermion compound.     

Synthesis, characterization, and optical properties of In2O3 semiconductor nanowires

In2O3 semiconductor nanowires were synthesized by the chemical vapor deposition method through carbon thermal reduction at 900 degrees C with 95% Ar and 5% O2 gas flow. The In2O3 nanowires were characterized by field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM), and photoluminescence spectroscopy (PL). For the first time, we observed the formation of corundum-type h-In2O3 nanowires and branched In2O3 nanowires. The PL spectra of In2O3 nanowires show strong visible red emission at 1.85 eV (670 nm) at low temperature, possibly caused by a small amount of oxygen vacancies in the nanowire crystal structure.     

Spin-frustrated trinuclear Cu(II) clusters with mixing of 2(S = 1/2) and S = 3/2 states by antisymmetric exchange. 1. Dzialoshinsky-Moriya exchange contribution to zero-field splitting of the S = 3/2 state

The mixing of the spin-frustrated 2(S = 1/2) and S = 3/2 states by the Dzialoshinsky-Moriya (DM) exchange is considered for the Cu 3(II) clusters with strong DM exchange coupling. In the antiferromagnetic Cu 3 clusters with strong DM interaction, the 2(S = 1/2)-S = 3/2 mixing by the in-plane DM exchange ( G x ) results in the large positive contribution 2 D DM > 0 to the axial zero-field splitting (ZFS) 2 D of the S = 3/2 state. The correlations between the ZFS 2 D DM of the excited S = 3/2 state, sign of G z and chirality of the ground-state were obtained. In the isosceles Cu 3 clusters, the in-plane DM exchange mixing results in the rhombic magnetic anisotropy of the S = 3/2 state. Large distortions result in an inequality of the pair DM parameters, that leads to an additional magnetic anisotropy of the S = 3/2 state. In the {Cu 3} nanomagnet, the in-plane DM exchange (Gx, Gy) mixing results in the 58% contribution 2 D DM to the observed ZFS 2 D of the S = 3/2 state. The DM exchange and distortions explain the experimental observation that the intensities of the electron paramagnetic resonance (EPR) transitions arising from the 2(S = 1/2) group of levels of the {Cu 3} nanomagnet are comparable to each other and are 1 order of magnitude weaker than that of the S = 3/2 state. In the ferromagnetic Cu 3 clusters, the in-plane DM exchange mixing of the excited 2(S = 1/2) and the ground S = 3/2 states results in the large negative DM exchange contribution 2 D DM' < 0 to the axial ZFS 2 D of the ground S = 3/2 state.     

The beta-dialdiminato ligand [{N(C6H3Pri(2)-2,6)C(H)}2CPh]-: the conjugate acid and Li, Al, Ga and In derivatives

The synthesis of the following crystalline complexes is described: [Li(L)(thf)2] (), [Li(L)(tmeda)] (), [MCl2(L)] [M=Al (), Ga ()], [In(Cl)(L)(micro-Cl)2Li(OEt2)2] (), [In(Cl)(L){N(H)C6H3Pri(2)-2,6}] (), [In(L){N(H)C6H3Pri(2)-2,6}2] (), [{In(Cl)(L)(micro-OH)}2] (), [L(Cl)In-In(Cl)(L)] () (the thf-solvate, the solvate-free and the hexane-solvate), [{In(Cl)L}2(micro-S)] () and [InCl2(L)(tmeda)] () ([L]-=[{N(C6H3Pri(2)-2,6)C(H)}2CPh]-). From H(L) (), via Li(L) in Et2O, and thf, tmeda, AlCl3, GaCl3 or InCl3 there was obtained , , , or , respectively in excellent yield. Compound was the precursor for each of , and [{InCl3(tmeda)2{micro-(OSnMe2)2}}] () by treatment with one () or two () equivalents of K[N(H)(C6H3Pri(2)-2,6)], successively Li[N(SiMe3)(C6H3Pri(2)-2,6)] and moist air (), Na in thf (), tmeda (), or successively tmeda and Me3SnSnMe3 (). Crystals of (with an equivalent of In) and were obtained from InCl or thermolysis of [In(Cl)(L){N(SiMe3)(C6H3Pri(2)-2,6)}] () {prepared in situ from and Li[N(SiMe3)(C6H3Pri(2)-2,6)] in Et2O}, respectively. Compound was obtained from a thf solution of and sulfur. X-Ray data for crystalline , , , , , and are presented. The M(L) moiety in each (not the L-free ) has the monoanionic L ligated to the metal in the N,N'-chelating mode. The MN1C1C2C3N2 six-membered M(L) ring is pi-delocalised and has the half-chair (, and ) or boat (, and ) conformation.     

镁掺杂对In2O3电导和气敏性能的影响

用共沉淀法制备了Mg2+掺杂的In2O3纳米粉,研究了镁掺杂对In2O3电导和气敏性能的影响.结果表明:MgO和In2O3间可形成有限固溶体In2-xMgxO3(0≤x≤0.40);MgIn×电离的空穴对材料导带电子的湮灭,使掺镁纳米粉的电导变得很小;n(Mg2+):n(In3+)=1:2共沉淀物于900℃下热处理4 h,用所得的纳米粉制作的传感器在320～370℃下,对45μmol/L C2H5OH的灵敏度达102.5,为相同浓度干扰气体Petrol的12倍多.