制备条件对PANI/PATP/Au和TiO_2-PANI/PATP/Au膜光电化学性能的影响

应用电化学方法在不同条件下制备聚苯胺 (PANI)膜和TiO2 -PANI复合膜 ,并对其光电化学性能进行研究 .实验表明 ,制备条件是影响膜光电化学性能的重要因素 .对氨基硫酚 (PATP)的组装有利于改善PANI膜的附着力 ;部分氧化态PANI膜的光电化学响应明显优于还原态和氧化态PANI膜的光电化学响应 ;部分氧化态PANI膜的厚度对其光电化学性能有一最佳值 ;热处理虽然有利于改善TiO2 的光电化学性能 ,但温度太高 ,将破坏PANI膜的表面结构 ,对于TiO2 -PANI复合膜有一最佳的热处理温度 .优化制备条件大可改善TiO2 -PANI复合膜和PANI膜的光电化学性能     

Ti/α-PbO2/β-PbO2电极电化学降解2-氯酚

采用电化学沉积法在Ti基底上制备了复合电极Ti/α-PbO2/β-PbO2,扫描电镜结果表明电极呈现由β-PbO2小晶体组成的菜花状微观形貌.所制电极在电化学降解环境污染物2-氯酚时表现出较高的电催化效率、较好的电极稳定性和较长的电极寿命.用正交实验优化了电化学降解2-氯酚的实验条件.在最优的实验条件(2-氯酚初始浓度50 mg/L,电解质0.1 mol/L Na2SO4,温度35oC,阳极电流密度20 mA/cm2)下电化学降解180 min后,2-氯酚的去除率达100%.动力学结果表明, Ti/α-PbO2/β-PbO2电极上2-氯酚的电化学氧化符合准一级动力学过程.     

α-MnO2微球的制备及其电化学电容性质

以Ag片作催化剂在室温下制备了具有较高比表面积(177m2/g)的电化学电容器材料MnO2。XRD测试和SEM分析表明,所制备的MnO2为纳米纤维组成的仙人球状微球结构的α-MnO2。交流阻抗、循环伏安、恒流充放电和循环寿命等电化学测试均表明,所合成的α-MnO2微球在1mol/LNa2SO4水溶液中具有良好的电化学电容性能,单电极比电容可达187.1F/g,经1000次循环后电极容量仍保持在90%以上。     

电化学沉积制备半导体CuInSe2薄膜

本文报道恒电位法在pH为1.35的Cu₂SO₄、SeO₂、In₂(SO₄)₃溶液中,在Ti电极上电化学沉积制备CuInSe₂纳米薄膜.研究络合剂柠檬酸和酒石酸对制备CuInSe₂纳米薄膜的影响.扫描电子显微镜(SEM)结果表明,加入络合剂后,电化学沉积的薄膜表面颗粒分布更均匀、致密.X射线衍射(XRD)分析显示,制备的CuInSe₂薄膜是黄铜矿和闪锌矿相的混和物,添加柠檬酸和酒石酸后,衍射峰增强,晶形变好.制备的薄膜颗粒尺寸大小在250nm左右,造成粒度增大的原因是由于颗粒的团聚作用.     

Ti/α-PbO_2/β-PbO_2电极电化学降解2-氯酚（英文）

采用电化学沉积法在Ti基底上制备了复合电极Ti/α-PbO 2/β-PbO 2,扫描电镜结果表明电极呈现由β-PbO 2小晶体组成的菜花状微观形貌.所制电极在电化学降解环境污染物2-氯酚时表现出较高的电催化效率、较好的电极稳定性和较长的电极寿命.用正交实验优化了电化学降解2-氯酚的实验条件.在最优的实验条件(2-氯酚初始浓度50 mg/L,电解质0.1 mol/L Na2SO4,温度35 oC,阳极电流密度20 mA/cm2)下电化学降解180 min后,2-氯酚的去除率达100%.动力学结果表明,Ti/α-PbO 2/β-Pb O2电极上2-氯酚的电化学氧化符合准一级动力学过程.     

相转移法制备LiNi1-xMnxO2及其电化学性能

相转移法制备LiNi1-xMnxO2及其电化学性能     

LiCoO2/LiMn2O4复合薄膜电极制备及其在高温下的电化学性能

LiCoO2/LiMn2O4复合薄膜电极制备及其在高温下的电化学性能;锂离子电池;表面包覆     

Cu2+离子掺杂钙锰矿的合成及电化学性质研究

采用不同方法制备出单一或掺杂Cu2+离子的钙锰矿, 分析了其隧道或者骨架结构中掺杂Cu2+离子的合成条件, 并应用粉末微电极考察了其电化学活性和稳定性. 单一或骨架中掺杂Cu2+离子的钙锰矿可在常压回流条件下制备; 隧道中掺杂Cu2+离子的钙锰矿须经高温高压热液反应合成, 且反应温度是影响产物纯度的主导因素. 钙锰矿在高pH值溶液中电化学稳定性较好; 骨架中掺杂Cu2+离子可提高钙锰矿的电化学活性和稳定性, 而隧道中掺杂Cu2+离子的钙锰矿电化学活性较低; 结合循环伏安法进一步证明了后者掺杂的Cu2+离子主要位于钙锰矿的隧道中.     

一步原位还原法制备WS2@Au量子点复合物及其传感应用

电化学传感器界面改造是提升其检测性能的重要途径.其中,增强电化学传感界面的生物相容性和导电性,是电化学传感器发展遇到的一个重大挑战.本文基于一步原位还原法制备的WS2@Au量子点(WS2@AuQDs),对玻碳电极表面进行功能化,用于氧化还原酶的固定,实现了高性能生物传感的构建.借助WS2@Au QDs良好的生物相容性及...     

单分散纳米Ni(OH)2的制备及其电化学性能

表面活性剂;单分散纳米Ni(OH)2的制备及其电化学性能     

RuO2电极的析氧活性研究

本文用XPS, UPS和电化学方法研究了RuO2电极的活怀中心组成及其在电解过程中的变化。结果表明, RuO2电极的活性中心为氧结构空位。在电解过程中,表层的氧结构空位不断减少, 由于RuO2电极析氧反应区域不断扩展和深入, 又暴露出新的氧结构空位, 但电极外表面的氧结构空位对电极析氧活性影响较大, 外表面氧结构空位为RuO2电极有效的活性中心。此外, 电极的腐蚀和剥落也是导致活性降低的原因之一。     

Photocatalytic activity of the RuO2-dispersed composite p-block metal oxide LiInGeO4 with d10-d10 configuration for water decomposition

The ruthenium oxide-loaded composite p-block metal oxide LiInGeO4 with d10-d10 configuration exhibited high photocatalytic activity for the overall splitting of water to produce H2 and O2 under UV irradiation. Changes in the photocatalytic activity with the calcination temperature of LiInGeO4, the amount of RuO2 loaded, and the states of RuO2 indicated that the combination of highly crystallized LiInGeO4 and a high dispersion of RuO2 particles resulted in high photocatalytic activity. Structurally, LiInGeO4 contained heavily distorted InO6 octahedra and GeO4 tetrahedra, generating a dipole moment inside. The high photocatalytic performance of RuO2-loaded LiInGeO4 supports the existing view that the photocatalytic activity correlates with the dipole moment. The DFT calculation showed that the top of the valence band (HOMO) was composed of the O 2p orbital while the bottom of the conduction band (LUMO) was formed by the hybridized In 5s5p + Ge 4s4p + O 2p orbitals. The highly dispersed conduction band, indicative of a high mobility of photoexcited electrons, was responsible for the high photocatalytic performance.     

光电化学反应的催化II.表面覆盖针状铱层对n-TiO2电极上光电化学过程的催化作用

借助于可换盘旋转环盘电极在含Ce[3+]酸性溶液中比较了n-TiO2电极上载多孔铱层前后的竞争光氧化过程,观察到当铱以高度分散的针状多孔透光层在TiO2电极表面分布时能够催化Ce[3+]的光电化学氧化,并据此讨论了催化光电化学反应的基本前题。     

Distinguishing homogeneous from heterogeneous catalysis in electrode-driven water oxidation with molecular iridium complexes

Molecular water-oxidation catalysts can deactivate by side reactions or decompose to secondary materials over time due to the harsh, oxidizing conditions required to drive oxygen evolution. Distinguishing electrode surface-bound heterogeneous catalysts (such as iridium oxide) from homogeneous molecular catalysts is often difficult. Using an electrochemical quartz crystal nanobalance (EQCN), we report a method for probing electrodeposition of metal oxide materials from molecular precursors. Using the previously reported [Cp*Ir(H(2)O)(3)](2+) complex, we monitor deposition of a heterogeneous water oxidation catalyst by measuring the electrode mass in real time with piezoelectric gravimetry. Conversely, we do not observe deposition for homogeneous catalysts, such as the water-soluble complex Cp*Ir(pyr-CMe(2)O)X reported in this work. Rotating ring-disk electrode electrochemistry and Clark-type electrode studies show that this complex is a catalyst for water oxidation with oxygen produced as the product. For the heterogeneous, surface-attached material generated from [Cp*Ir(H(2)O)(3)](2+), we can estimate the percentage of electroactive metal centers in the surface layer. We monitor electrode composition dynamically during catalytic turnover, providing new information on catalytic performance. Together, these data suggest that EQCN can directly probe the homogeneity of molecular water-oxidation catalysts over short times.     

Ni/Ag2O/RuO2-Pt阴极制备与析氢性能

以三氯化钌和氯铂酸为源物质,用溶胶凝胶法制备Ni/Ag2O/RuO2-Pt复合阴极,研究了不同涂覆液AgNO3浓度和热处理温度对该阴极析氢性能的影响.采用SEM-EDS、XRD和XPS观察阴极的表面形貌、表征其组分,结果表明,Ni/Ag2O/RuO2-Pt复合阴极表面致密,粗糙度大且裂纹少.电化学测量表明,在11 mol.L-1NaOH(90℃)溶液、0.3 A.cm-2电流密度下,Ni/Ag2O/RuO2-Pt复合阴极的析氢电位比纯Ni电极正移484 mV;交换电流密度是纯Ni电极的10倍.该阴极制备工艺简单,析氢活性高,有望降低氯碱工业的能耗.     

Synthesis and characterization of heterometallic clusters (Ir2Rh, Ir2W, Rh3) Containing 1,2-dicarba-closo-dodecaborane(12)-1,2-dithiolate chelate ligands, [(B10H10)C2S2]2-

The 16-electron half-sandwich complex [Cp*Ir[S2C2(B10H10)]] (Cp* = eta5-C5Me5) (1a) reacts with [[Rh(cod)(mu-Cl)]2] (cod = cycloocta-1,5-diene, C8H12) in different molar ratios to give three products, [[Cp*Ir[S2C2(B10H9)]]Rh(cod)] (2), trans-[[Cp*Ir[S2C2(B10H9)]]Rh[[S2C2(B10H10)]IrCp*]] (3), and [Rh2(cod)2[(mu-SH)(mu-SC)(CH)(B10H10)]] (4). Complex 3 contains an Ir2Rh backbone with two different Ir-Rh bonds (3.003(3) and 2.685(3) angstroms). The dinuclear complex 2 reacts with the mononuclear 16-electron complex 1a to give 3 in refluxing toluene. Reaction of 1a with [W(CO)3(py)3] (py = C5H5N) in the presence of BF3.EtO2 leads to the trinuclear cluster [[Cp*Ir[S2C2(B10H10)]]2W(CO)2] (5) together with [[Cp*Ir(CO)[S2C2(B10H10)]]W(CO)5] (6), and [Cp*Ir(CO)[S2C2(B10H10)]] (7). Analogous reactions of [Cp*Rh[S2C2(B10H10)]] (1 b) with [[Rh(cod)(mu-Cl)]2] were investigated and two complexes cis-[[Cp*Rh[S2C2(B10H10)]]2Rh] (8) and trans-[[Cp*Rh[S2C2(B10H10)]]2Rh] (9) were obtained. In refluxing THF solution, the cisoid 8 is converted in more than 95 % yield to the transoid 9. All new complexes 2-9 were characterized by NMR spectroscopy (1H, 11B NMR) and X-ray diffraction structural analyses are reported for complexes 2-5, 8, and 9.     

Coordination solids derived from Cp*M(CN)3- (M = Rh,Ir)

Solutions of Rh2(OAc)4 and Et4N[Cp*Ir(CN)3] react to afford crystals of the one-dimensional coordination solid [Et4N[Cp*Ir(CN)3][Rh2(OAc)4]]. This reaction is reversed by coordinating solvents such as MeCN. The structure of the polymer consists of helical anionic chains containing Rh2(OAc)4 units linked via two of the three CN ligands of Cp*Ir(CN)3-. Use of the more Lewis acidic Rh2(O2CCF3)4 in place of Rh2(OAc)4 gave purple [(Et4N)2[Cp*Ir(CN)3]2[Rh2(O2CCF3)4]3], whose insolubility is attributed to stronger Rh-NC bonds as well as the presence of cross-linking. The species [[Cp*Rh(CN)3][Ni(en)n](PF6)] (n = 2, 3) crystallized from an aqueous solution of Et4N[Cp*Rh(CN)3] and [Ni(en)3](PF6)2; [[Cp*Rh(CN)3][Ni(en)2](PF6)] consists of helical chains based on cis-Ni(en)(2)2+ units. Aqueous solutions of Et4N[Cp*Ir(CN)3] and AgNO3 afforded the colorless solid Ag-[Cp*Ir(CN)3]. Recrystallization of this polymer from pyridine gave the hemipyridine adduct [Ag[Ag(py)][Cp*Ir(CN)3]2]. The 13C cross-polarization magic-angle spinning NMR spectrum of the pyridine derivative reveals two distinct Cp* groups, while in the pyridine-free precursor, the Cp*'s appear equivalent. The solid-state structure of [Ag[Ag(py)][Cp*Ir(CN)3]2] reveals a three-dimensional coordination polymer consisting of chains of Cp*Ir(CN)3- units linked to alternating Ag+ and Ag(py)+ units. The network structure arises by the linking of these helices through the third cyanide group on each Ir center.     

RuO2/电解液界面表面酸碱平衡与表面配位平衡

本文发现胶休“聚合电解质”模型较好地适用于RuO_2按此模型计算了RuO_2/电解液界面表面酸碱平衡常数和表面配位平衡常数,从而得出RuO_2的零电荷点。     

电子和空间位阻效应促进铱配合物催化1-丁醇经Guerbet反应选择制备2-乙基己醇

2-乙基己醇是一种增塑剂醇,可用于合成增塑剂、表面活性剂和溶剂等诸多化工领域.目前工业上2-乙基己醇的合成是以化石资源丙烯为原料,与氢气和一氧化碳通过氢甲酰化反应制备1-丁醛,后者经羟醛缩合和催化加氢反应生成2-乙基己醇.由生物质发酵产生的1-丁醇为原料,只需要经Guerbet反应可一步直接生成2-乙基己醇.比较而言,Guerbet反应路线步骤更少,且1-丁醇原位脱氢产生的氢为氢源,无需额外氢,因此比化石资源丙烯路线对环境友好.目前,文献报道的非均相催化1-丁醇Guerbet反应条件苛刻(如温度>170 oC),副产物多(如烯烃、醚和高碳醇等),且均相催化剂的活性低.本文报道了一类Cp*Ir(Cp*为1,2,3,4,5-五甲基环戊二烯基)配合物用于该Guerbet反应.当Cp*Ir配合物的配体上修饰给电子基N,N-二甲基氨基和邻羟基时,Cp*Ir配合物的催化活性增强,催化剂的转化数最高达到了14047.当氢氧化钾和Cp*Ir配合物(配体上修饰了N,N-二甲基氨基和邻羟基官能团)在1-丁醇中的浓度分别为1.7 mol％和0.04 wt％时,在130 oC反应48 h,产物2-乙基己醇收率为23.9％,选择性为89.5％.核磁(NMR)研究结果表明,Cp*Ir配合物配体上的邻羟基与氢氧化钾反应脱除质子,生成了羰基结构配体配位的Cp*Ir配合物,继续催化1-丁醇脱氢反应.机理研究表明,中间产物2-乙基己醛α-碳上乙基的位阻效应和2-乙基己烯醛本身的共轭效应抑制了其继续发生羟醛反应,从而提高了目标产物的选择性.     

光电化学反应的催化I.大颗粒金岛对n-TiO2电极上光电化学过程的催化作用

用溅射、光还原及电沉积法在n-TiO2单晶电极表面上形成了大颗粒金岛,测量了这些电极和纯金电极在H2SO4溶液以及含有Fe[3+]/Fe[2+]的酸溶液中的光电化学极化行为。通过分析和比较这些曲线,确定了大颗粒金岛与n-TiO2单晶的接触具有欧姆结性质。并借助于可换盘旋转环盘电极,在含Ce[3+]的酸溶液中测量了裸TiO2电极及载金TiO2电极上Ce[3+]的竞争光电化学氧化。证实了以大岛形式在TiO2电极表面上分布的催化剂只能催化暗反应,而不能催化光电化学反应。