Sb2S3纳米粒子修饰ZnO纳米片微纳分级结构的光电化学性能

采用恒电位方法,选择氯化钾和乙二胺(EDA)为添加剂,在氧化铟锡(ITO)导电玻璃上制备了高度有序的ZnO纳米片阵列,通过二次电沉积得到了ZnO纳米片上生长纳米棒的微纳分级结构.利用化学浴沉积法在ZnO基底上沉积Sb₂S₃纳米粒子制备出了Sb₂S₃/ZnO纳米片壳核结构和Sb₂S₃/ZnO微纳分级壳核结构.利用扫描电子显微镜(SEM)、X射线衍射(XRD)、紫外-可见(UV-Vis)吸收光谱、瞬态光电流等对其形貌、结构组成和光电化学性能进行了表征和分析.结果表明, Sb₂S₃/ZnO纳米片上生长纳米棒分级壳核结构的光电流明显高于Sb₂S₃/ZnO纳米片壳核结构.在Sb₂S₃/ZnO纳米片壳核结构和Sb₂S₃/ZnO微纳分级壳核结构的基础上旋涂一层P3HT薄膜形成P3HT/Sb₂S₃/ZnO复合结构,以上述复合结构薄膜为光活性层组装成杂化太阳电池,其中, P3HT/Sb₂S₃/ZnO分级壳核结构杂化太阳电池的能量转换效率最高,达到了0.81%.     

制备二氧化钛分枝纳米棒阵列结构以提高聚合物杂化太阳电池的性能

分别采用一步水热法和两步水热法在导电玻璃(FTO)上制备了二氧化钛(TiO₂)纳米棒(NR)阵列和TiO₂分枝纳米棒(B-NR)阵列。 利用低温化学浴沉积法(CBD)在TiO₂纳米棒阵列(NRA)和TiO₂分枝纳米棒阵列(B-NRA)基底上沉积Sb₂S₃纳米粒子(NPs)。 接着分别旋涂聚-3已基噻吩(P3HT)和2,2'7,7'-四-(二甲氧基二苯胺)螺芴(Spiro-OMeTAD)组装成TiO₂(NRA)/Sb₂S₃/P3HT/Spiro-OMeTAD和TiO₂(B-NRA)/Sb₂S₃/P3HT/ Spiro-OMeTAD为光活性层的杂化太阳电池。 结果表明,由TiO₂(NRA)/Sb₂S₃/P3HT/Spiro-OMeTAD复合膜结构组装的杂化太阳电池的光电转换效率(PCE)是2.92%,而由TiO₂(B-NRA)/Sb₂S₃/P3HT/Spiro-OMeTAD复合膜结构组装的杂化太阳电池的PCE提高到了4.67%。     

热退火气氛对溶液法制备的Sb2S3薄膜组成、结构及光伏性能的影响

采用化学浴(CBD)法在TiO₂薄膜表面制备结晶性Sb₂S₃膜层, 获得了TiO₂/Sb₂S₃平板异质结, 并结合聚[2,6-{4,4-双-(2-乙基己基)-4H-环戊并[2,1-b;3,4-b']-二噻吩}-交替-4,7-(2,1,3-苯并噻二唑)](PCPDTBT)空穴传输层和MoO₃电极界面修饰层, 制备了FTO/TiO₂/Sb₂S₃/PCPDTBT/MoO₃/Au平板结构太阳能电池, 研究了CBD方法中热退火气氛对Sb₂S₃薄膜的组成、 结构及光伏性能的影响. 结果表明, 在N₂气氛下退火时, 所得的Sb₂S₃膜层不致密且含有Sb₂O₃杂相, 电池效率仅为0.90%; 而在N₂-S气氛下退火时, 硫会与杂相Sb₂O₃发生反应生成Sb₂S₃, 进而得到纯净、 致密、 平整的结晶Sb₂S₃膜层. 在平板结构太阳能电池中, 光生空穴对电池光电流的产生有明显的贡献; 随着Sb₂O₃杂相的消除, Sb₂S₃薄膜中载流子的复合减少且传输速率增大, 使太阳能电池器件中电子与空穴的收集效率和短路电流显著提高, 电池效率提高了1.34倍, 达到2.04%.     

回流法合成硫化锑纳米棒及其光催化性能研究

以三氯化锑(SbCl₃)、硫粉(S)和硼氢化钠(NaBH₄)为原料, 1,2-丙二醇(C₃H₈O₂)作溶剂, 用回流法成功合成了Sb₂S₃纳米棒. 用XRD, EDS, SEM, TEM, HRTEM, SAED以及UV-Vis等手段对所制备产品的晶型、成分、形貌和光学特性进行了表征|以太阳光为光源、亚甲基蓝为目标降解物评价了Sb₂S₃纳米棒的光催化活性. 结果表明, 经186 ℃回流15 h可得到直径约为78～180 nm、长度达2～5 μm的正交晶系的Sb₂S₃单晶纳米棒. 经计算, 其晶胞参数a＝1.124 nm, b＝1.138 nm, c＝0.384 nm. UV-Vis分析表明, Sb₂S₃纳米棒为半导体材料, 其带隙能量为1.52 eV. 光催化性能测试表明, 所制备的Sb₂S₃纳米棒在太阳光下对亚甲基蓝具有较高的光催化降解率, 经20 min降解, 亚甲基蓝的降解率达84.31%, 表现出明显的可见光活性. 加入的PVP对控制Sb₂S₃的形貌有重要的作用. 另外, 还讨论了Sb₂S₃ 纳米棒可能的形成机理.     

3D ZnIn2S4微球/1D TiO2纳米带异质结构的光催化降解和还原性能

首先采用溶剂热法和高温煅烧法制备1D TiO₂纳米带,其次利用溶剂热法将1D TiO₂纳米带均匀地穿插到片层结构组装而成的3D ZnIn₂S₄微球中,所形成的异质结构能有效抑制光生电子-空穴的复合。二元ZnIn₂S₄微球/TiO₂纳米带复合光催化剂在高浓度染料罗丹明B(RhB)的光降解和Cr(VI)的光还原实验中表现出优异的性能。在模拟太阳光照射下,ZnIn₂S₄/TiO₂纳米带光催化降解RhB和还原Cr(VI)的效率相较于纯TiO₂颗粒(10%,22%)、TiO₂纳米带(45%,40%)、ZnIn₂S₄(62%,65%)、ZnIn₂S₄/TiO₂颗粒(90%,91%)分别提高至100%和100%。最后,通过紫外-可见...     

CdSe纳米晶/共轭聚合物太阳电池的制备与性能研究

采用有机金属液相法制备了平均粒径为5 nm的CdSe纳米微球(ns-CdSe), 并将其与共轭聚合物(MEH-PPV或P3HT)共混制备了太阳电池器件. 透射电镜(TEM)、紫外-可见吸收光谱(UV-Vis)及荧光光谱(PL)研究结果表明, CdSe纳米晶呈均匀的球状颗粒, 在近红外区具有良好的吸收和荧光性能; 加入CdSe纳米晶能够有效地淬灭共轭聚合物的荧光. 在AM1.5模拟太阳光(光强为100 mW/cm2)照射下, ns-CdSe/MEH-PPV共混体系太阳电池器件性能测试结果为: 短路电流ISC为1.56 mA/cm2, 开路电压VOC为0.75 V, 填充因子FF为34.5％, 光电转换效率η为0.40%; 对于ns-CdSe/P3HT共混体系, 其ISC为1.93 mA/cm2, VOC为0.65 V, FF为38.4%, η为0.48%.     

Unraveling the influence of interface defects on antimony trisulfide solar cells

Antimony trisulfide(Sb₂S₃) solar cells suffer from large open circuit voltage deficits due to their intrinsic defects which limit the power conversion efficiency.Thus,it is important to elucidate these defects’ origin and defects at the interface.Here,we discover that sulfide radical defects have a significant impact on the performance of Sb₂S₃ solar cells.Moreover,it has been illustrated that these defects at the CdS/Sb₂S₃interfa...     

盐酸后处理制备高效制氢光催化剂Zn2In2S5

采用水热法制备了ZnIn₂S₄固溶体, 并通过用盐酸对其进行后处理获得了系列Zn_mIn₂S_m+3(m≥2, 整数)固溶体. 通过X射线衍射(XRD)、 扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 X射线光电子能谱(XPS)、 紫外-可见漫反射光谱(UV-Vis DRS)、 荧光光谱(PL)和电化学测试对催化剂的组成、 结构和性能进行了表征. 研究了系列固溶体可见光光催化制氢活性. 结果表明, ZnIn₂S₄固溶体经0.5 mol/L HCl处理后能转化为Zn₂In₂S₅固溶体, 其制氢活性为ZnIn₂S₄固溶体的2.2倍, 并且具有良好的稳定性.     

2D/3D ZnIn2S4/TiO2复合物的原位构筑及其提高的光催化性能

通过高温煅烧和油浴的方法构筑二维/三维(2D/3D) ZnIn₂S₄/TiO₂异质结, 应用于光催化降解罗丹明B (RhB)和四环素(TC), 来研究异质结的构筑对TiO₂可见光响应范围和光生载流子对分离效率的影响. 结果表明, TiO₂维持了MOFs的形貌, 显示窄的可见光响应范围和高的光生电荷复合率, 与ZnIn₂S₄纳米片复合后, TiO₂的比表面积增大, 光催化活性位点增多. 带隙宽度也由TiO₂的3.23 eV减小到ZnIn₂S₄/TiO₂-II的2.52 eV, 从而获得了更宽的可见光响应范围. 能带结构表明ZnIn₂S₄/TiO₂是type II型异质结, 提高了光生载流子对的分离与转移效率. 在可见光照射下, ZnIn₂S₄/TiO₂-II显示了最高的RhB光催化降解效率(93%), 分别是TiO₂和ZnIn₂S₄的18和2倍. 同时, ZnIn₂S₄/TiO₂-II也显示出比TiO₂和ZnIn₂S₄更高的TC降解效率(90%). 循环实验表明ZnIn₂S₄/TiO₂-II能保持良好的稳定性, 经5次循环实验后仍能降解83%的RhB. 研究表明基于MOFs衍生的TiO₂构筑2D/3D ZnIn₂S₄/TiO₂异质结是提高TiO₂光催化性能的一条有效途径.     

具有分级纳米结构的In2S3/CdIn2S4在可见光下催化苯甲胺的氧化偶联反应

采用以太阳光为能源、半导体材料为催化剂的催化体系将胺类化合物转化为相应的亚胺类化合物的方法是一种理想的有机合成手段.为了探索这类反应更温和的反应条件及更清晰的反应机理，本工作以NH₂-MIL-68（In）和硫脲为前驱体制备了In₂S₃分级纳米管，并进一步采用热离子交换的方法制备了In₂S₃/CdIn₂S₄纳米管复合材料.采用粉末X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、高分辨透射电子显微镜（HRTEM）、紫外-可见漫反射光谱（UV-vis DRS）、荧光光谱（PL）和电化学阻抗谱（EIS）等分析手段对催化剂的结构、形貌、光电性质等进行了表征.实验结果显示，In₂S₃和CdIn₂S₄间有效异质结降低了In₂S₃/CdIn₂S₄复合材料的光生载流子的复合效率，使In₂S₃/CdIn₂S₄具有较高的催化活性.催化剂的活性测试实验结果证明，In₂S₃和CdIn₂S₄间有效异质结和分级结构间的协同作用使In₂S₃/CdIn₂S₄纳米复合材料可作为一种有效的光催化剂催化氧化苯甲胺的偶联反应.活性物种捕获实验证明该反应是由光生空穴（h⁺）引发的.此外，此研究发现苯甲胺的氧化偶联反应同时可以在氧气或氮气条件下发生，打破了该反应必须要有氧气参与的束缚，拓展了苯甲胺氧化偶联反应的适用范围.循环实验结果显示，催化剂可循环使用五次，证明该催化剂具有较好的稳定性.     

微波辅助快速制备2D/1D ZnIn2S4/TiO2 S型异质结及其光催化制氢性能

The threat and global concern of energy crises have significantly increased over the last two decades. Because solar light and water are abundant on earth, photocatalytic hydrogen evolution through water splitting has been considered as a promising route to produce green energy. Therefore, semiconductor photocatalysts play a key role in transforming sunlight and water to hydrogen energy. To date, various photocatalysts have been studied. Among them, TiO₂ has been extensively investigated because of its non-toxicity, high chemical stability, controllable morphology, and high photocatalytic activity. In particular, 1D TiO₂ nanofibers (NFs) have attracted increasing attention as effective photocatalysts because of their unique 1D electron transfer pathway, high adsorption capacity, and high photoinduced electron–hole pair transfer capability. However, TiO₂ NFs are considered as an inefficient photocatalyst for the hydrogen evolution reaction (HER) because of their disadvantages such as a large band gap (~3.2 eV) and fast recombination of photoinduced electron–hole pairs. Therefore, the development of a high-performance TiO₂ NF photocatalyst is required for efficient solar light conversion. In recent years, several strategies have been explored to improve the photocatalytic activity of TiO₂ NFs, including coupling with narrow-bandgap semiconductors (such as ZnIn₂S₄). Recently, microwave (MW)-assisted synthesis has been considered as an important strategy for the preparation of photocatalyst semiconductors because of its low cost, environment-friendliness, simplicity, and high reaction rate. Herein, to overcome the above-mentioned limiting properties of TiO₂ NFs, we report a 2D/1D ZnIn₂S₄/TiO₂ S-scheme heterojunction synthesized through a microwave (MW)-assisted process. Herein, the 2D/1D ZnIn₂S₄/TiO₂ S-scheme heterojunction was constructed rapidly by using in situ 2D ZnIn₂S₄nanosheets decorated on 1D TiO₂ NFs. The loading of ZnIn₂S₄ nanoplates on the TiO₂ NFs could be easily controlled by adjusting the molar ratios of ZnIn₂S₄ precursors to TiO₂ NFs. The photocatalytic activity of the as-prepared samples for water splitting under simulated solar light irradiation was assessed. The experimental results showed that the photocatalytic performance of the ZnIn₂S₄/TiO₂ composites was significantly improved, and the obtained ZnIn₂S₄/TiO₂ composites showed increased optical absorption. Under optimal conditions, the highest HER rate of the ZT-0.5 (molar ratio of ZnIn₂S₄/TiO₂= 0.5) sample was 8774 μmol·g^-1·h^-1, which is considerably higher than those of pure TiO₂ NFs (3312 μmol·g^-1·h^-1) and ZnIn₂S₄nanoplates (3114 μmol·g^-1·h^-1) by factors of 2.7 and 2.8, respectively. Based on the experimental data and Mott-Schottky analysis, a possible mechanism for the formation of the S-scheme heterojunction between ZnIn₂S₄ and TiO₂ was proposed to interpret the enhanced HER activity of the ZnIn₂S₄/TiO₂heterojunctionphotocatalysts.      

钛基金属氧化物电极制备及其氨氮废水降解性能

采用热分解方法制备了4种电极钛基金属氧化物：Ti/SnO₂+Sb₂O₃、Ti/SnO₂+Sb₂O₃/SnO₂+IrO₂、Ti/SnO₂+Sb₂O₃/SnO₂+RuO₂和Ti/SnO₂+Sb₂O₃/SnO₂+CeO₂. X-射线衍射分析表明Ti/SnO₂+Sb₂O₃/SnO₂+CeO₂电极的CeO₂晶体结构完好,连续工作较长时间电极表面没有明显析氧. 使用该电极电解氧化氨氮模拟废水（降解2 h）,氨氮模拟废水从高浓度（500 mg·L^-1）降解为较低浓度（180 mg·L^-1）,降解效率可达64%,电解活性最佳.     

Z型光催化剂Sb2WO6/g-C3N4的制备及光催化性能

通过水热反应合成了Sb₂WO₆改性的g-C₃N₄复合材料(Sb₂WO₆ /g-C₃N₄). 通过X射线衍射(XRD)、 扫描电子显微镜(SEM)、 紫外-可见漫散射反射光谱(UV-Vis DRS)和光致发光光谱(PL)等表征了样品的性质. 结果表明, Sb₂WO₆在g-C₃N₄的表面上生长, 并且复合材料光吸收能力有一定的增强, 光生电子-空穴的重组率降低. 通过罗丹明B(RhB)的光降解评价了Sb₂WO₆/g-C₃N₄复合材料的光催化性能. 结果表明, 模拟日光下Sb₂WO₆质量分数为10%的Sb₂WO₆/g-C₃N₄复合材料在60 min内对RhB的降解率为99.3%, 高于纯g-C₃N₄和Sb₂WO₆. Sb₂WO₆/g-C₃N₄复合材料的这种高度增强的光催化活性主要归因于强的界面相互作用促进了光生电子-空穴分离和迁移. 添加自由基清除剂的实验结果表明, ·O^2-和h⁺是光催化反应中的主要活性物质. Sb₂WO₆/g-C₃N₄复合材料在几个反应周期内表现出优异的稳定性. 根据实验结果提出了一种可能的Z型光催化机理.     

Oxygen potential and phase equilibria in the Te-Sb2O3-Sb2O4 pseudoternary part of the Sb-Te-O system at elevated temperatures

Employing the electrochemical cells with the solid oxide electrolyte

Kanthal + Re, Te(l), TeO₂(s)O⁻² air, Pt

Pt + Re, Sb₂O₃(s), Sb₂O₄(s)O⁻² air, Pt

Pt + Re, Sb₂O₃(s), Sb₂O₄(s), Te(l)O⁻² air, Pt

the equilibrium oxygen potential in the pseudobinary Te-TeO₂, Sb₂O₃-Sb₂O₄ and in the Sb₂O₃-Sb₂O₄-Te pseudoternary systems was determined in the temperature range 700-1173 K. In addition, the pseudobinary sections Sb₂O₃-Te, Sb₂O₃-Sb₂O₄ (1:1)-Te and Sb₂O₄-Te were examined by DTA in the temperature range 500-1300 K. Using these results the evolution of the pseudoternary system with temperature can be suggested. It was found that, at 718 K, a ternary eutectic with a composition close to pure Te appears in the system. At a higher temperature, 920 K, another liquid phase is formed, which is characteristic of the ternary four-phase equilibrium L₂ + Sb₂O₄(s) + Sb₂O₃(s) = L₁.     

Hydrothermal Synthesized Co-Ni3S2 Ultrathin Nanosheets for Efficient and Enhanced Overall Water Splitting

We used the one-step hydrothennal controlled synthesis method for Co-Ni3S2 ultrathin nanosheets grown directly on nickel foam(NF).The as-synthesized Co-Ni3S2/NF showed eiilianced activities in the hydrogen evolution reaction(HER),oxygen evolution reaction(OER)and better overall water splitting(OWS)efficiency than the iin-doped Ni3S2/NF.the voltage of Co-Ni3S2/NF for OWS was only 1.58 V at the current density of 10 niA/cm^2 and with long time(>30 h)current output during the current-density(i-t)test.The good i-t pertonnance was also observed in both HER and OER processes.Additionally,the Co-Ni3S2/NF showed a large current density(>1A/cm^2)for both HER and OER.Wlien the current densities reached 100 and 1000 mA/cm^2,the required overpotentials tor Co-Ni3S2/NF were 0.35 and 0.75 V for OER and 0.30 and 0.85 V for HER.Therefore,after introducing Co,the activity of Ni3S2-based material was strongly enhanced.     

皱褶表面介孔镍钴硫化物微球的制备及其超电性能

通过一步水热法分别合成了α-NiS、Co₃S₄和CoNi₂S₄纳米介孔电极材料,并研究了其电化学性能。 X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)研究表明,介孔硫化物是由单相纳米颗粒堆叠组装而成,其中二元系的CoNi₂S₄由纳米片自组装形成了具有皱褶表面的微球形貌。 电化学性能研究表明,二元系的CoNi₂S₄比α-NiS、Co₃S₄具有更高的比电容、更佳的倍率特性和优异的循环稳定性。 在扫描速率为5 mV/s时,CoNi₂S₄材料在6 mol/L KOH电解液中比电容高达1678.3 F/g,优于α-NiS (787.4 F/g)和Co₃S₄(1532.7 F/g),在扫描速率从5 mV/s增加到100 mV/s时,其电容保持率为45.8%,比α-NiS(30.2%)和Co₃S₄(29.3%)高出约15%。 在15A/g的电流密度下,经过900次循环充-放电后,二元系的CoNi₂S₄的电容仍保持在96.3%,库伦效率保持在94.3%左右,说明镍钴双金属硫化物具有优异的循环稳定性能和充放电可逆性。     

Electronic Structure Effect of Polythiophene Derivatives and Nano N-Zn-Ag/TiO2 on Performance of Organic Thin Film Solar Cell

Nanocrystal N-Zn-Ag/TiO₂ powders were prepared with N-Zn/TiO₂ by photo deposition method. A series of pure polymers P3HT[poly(3-hexylthiophene)], P3OT[poly(3-octylthiophene)], P3DT[poly(3-decylthiophene)] and P3DDT[poly(3-dodecylthiophene)], was synthesized, which were used to synthesize p-n type semiconductor materials P3HT/N-Zn-Ag-TiO₂, P3OT/N-Zn-Ag-TiO₂, P3DT/N-Zn-Ag-TiO₂ and P3DDT/N-Zn-Ag-TiO₂ by in situ che-mical method. X-Ray diffraction(XRD) and infrared(IR) spectroscopy showed the structure of the polymers and complexes. Ultraviolet-visible(UV-Vis) spectra and cyclic voltammograms(CV) showed the optical and electronic performance of the polymers and complexes. Two new single and double organic thin film heterojunction solar cells were prepared with the above mentioned synthesized powders as raw materials. Current-voltage(I-V) measurements indicate that the conversion efficiency of the single organic thin film heterojunction solar cell is higher than that of the double organic thin film heterojunction solar cells. Single organic thin film heterojunction solar cells based on P3DT/N-Zn-Ag-TiO₂ can get a photoelectric conversion efficiency of 0.0408%. The performance of electronic transform between electron donor and acceptor on organic thin film solar cells was researched.