ZnO基光电极的构筑及其光电催化水分解性能研究进展

光电催化水分解制取氢气是最理想的制氢技术之一。光电极材料作为光电催化水分解反应系统最核心的部分,决定着太阳能到化学能的转换效率。氧化锌（ZnO）半导体因具有较低的超电势、高的电子迁移速率和价格低廉等优点,引起了广泛关注。然而,ZnO半导体的禁带较宽、电子-空穴易于复合和表面水氧化反应动力学缓慢,阻碍了其高效利用太阳能和实现理论效率。本文从ZnO的微纳结构和表界面修饰两个方面出发,综述了近年来ZnO基光电极的构筑策略及其光电催化性能的研究进展。首先阐述了ZnO的微观形貌和缺陷对光电性质的影响。然后总结了元素掺杂、量子点敏化、贵金属沉积、异质结构造和共催化剂沉积等策略对ZnO基半导体的表界面的构筑及对光电催化性能的影响。最后对未来高效ZnO基半导体光电极研究方向进行了展望,具体包括5个方面：ZnO表面改性;在原子水平构筑复合半导体催化剂的相界面;用廉价双金属或多金属纳米颗粒取代纯贵金属Au、Ag和Pt纳米颗粒;构建高效的电催化剂助剂;在ZnO半导体和助剂界面引入空穴储存层或电子堵塞层。     

CuBi2O4光电极改性策略的研究

选择低成本、高效、稳定的半导体光电极,是实现经济可行的光电催化转换能源的关键步骤.由于具有相对的光稳定性,Cu基过渡金属三元氧化物因作为p型半导体光电阴极材料而受到关注.其中,CuBi2O4作为一种窄带隙的PEC光阴极候选材料受到了广泛的关注.     

福建物构所卤化铅杂化半导体材料研究获进展

正卤化铅钙钛矿无机-有机杂化材料在光电子器件、太阳能电池、催化、离子交换和快离子导体等方面具有重要应用价值,作为新型光伏材料备受科学家关注,其光电转换效率已迅速刷新到20%,并有望达到晶体硅电池25%的水平。这类材料的半导体性能主要来源于杂化材料中的无机骨架部分,目前研究主要集中在     

二氧化钛包覆氧化锌纳米阵列光阳极的制备与性能

采用直流反应磁控溅射工艺,在ZnO纳米阵列的表面实现TiO2包覆,作为染料敏化太阳能电池光阳极,研究TiO2--ZnO核壳结构的形成机理和制备工艺对其光电性能的影响。利用X射线衍射仪、扫描电子显微镜、能谱分析仪表征光阳极材料的成分与结构。测试电池组件的伏安特性曲线、电压-时间曲线和电化学阻抗谱,分析TiO2包覆对电子传输性能和光电转换效率的影响机理。结果表明:磁控溅射制备的TiO2颗粒完整地包覆ZnO纳米阵列,使得纳米棒表面形貌由六棱柱向圆柱状转变,间隙变窄,直径较ZnO纳米阵列有所增加,阵列有序度得到改善。随着延长染料吸附时间和TiO2包覆,光阳极界面电子传输阻抗显著增加,光生电子的寿命也得到提高。经过包覆的光阳极能够作为阻挡层钝化表面缺陷,抑制复合的发生,从而提高开路电压和填充因子。经过包覆的光阳极其光电转换效率相对于纯ZnO纳米阵列提高了132%。     

配体诱导制备NM88(D)/COF-OMe复合材料及可见光芬顿联合降解抗生素磺胺甲嘧啶研究

基于配体诱导界面生长策略,制备了具有优异光芬顿降解性能与稳定性的NM88（D）/COF-OMe复合材料,并对该材料的结构形貌与光电性能进行表征。表征结果说明：DMTP的锚定能够诱导复合材料内部形成紧密连接的异质界面,并提高COF-OMe在NM88（D）表面的分散度,提升该材料的比表面积、可见光吸收能力和光生载流子分离能力,从而增强复合材料的光催化能力。光芬顿降解性能测试表明：NM88（D）/COF-OMe对磺胺甲嘧啶（SMR）的降解速率常数为0.0658 min^-1,明显高于原始材料和其他已报道的催化剂。经循环使用10次后复合材料的降解率仍能保持初始态的95%以上,表明NM88（D）/COF-OMe具有良好的结构稳定性。最后,对复合材料光芬顿降解SMR的催化机理进行推导,NM88（D）/COF-OMe优异的催化能力归因于异质界面的存在提升了光生载流子分离效率并促使·OH高效生成。     

超微粉二氧化钛和掺杂三氧化二铁光催化剂的表面光电压谱研究

基于表面光伏效应测得的表面光电压谱在半导体表面化学物理的研究中早已获得极为广泛的应用。近年来,我们实验室成功地将这一技术应用于复相光催化的研究中,如发现表面光伏信号是半导体多晶粉末光催化剂具有活性的必要条件,光电压信号愈强光催化活性愈高,而且二者存在半定量的关系。这些结果启发我们,表面光伏技术有可能发展成为一种快速评估光催化剂的有效方法。鉴于超微粉光催化性能的研究具有很重要的     

有机化合物表面光电压谱的研究

半导体与金属接触处产生表面势垒,当光照射在样品与金属的接触界面上时,在光照面和非光照面之间建立起电位差,记录这个电位差和入射光波长的关系得到表面光电压谱。表面光电压谱反映材料的光吸收性质和电子的带-带跃迁,同时又受到光生载流子寿命的影响。应用表面光电压技术已经测量了单晶半导体的光伏效应,少数载流子的扩散长度以及表面态等。近来,王德军等用表面光电压谱的方法研究了无机半导体粉末光催化剂的活性。     

有机-无机半导体复合体系中光诱导电子转移及光电转换性质的研究

由于纳米材料技术和有机,无机复合材料技术的引入,染料敏化纳晶TiQ薄膜光电化学太阳能电池以较高的能量转换效率,并以低价,清洁,稳定性好,性能优异等特点而成为一种大有应用前景的新型太阳能电池．其中,光诱导电子转移、能量传递是发挥其光电转换功能的关键过程．本论文围绕反胶束中纳米CdS的制备和表征及界面电荷转移、联吡啶钌的光物理性质和光电转换性质等进行了研究,得到的结论如下．     

染料敏化太阳能电池中TiO_2光阳极的包覆效果

采用原位包覆和浸泡包覆在染料敏化太阳能电池的TiO2光阳极表面包覆了一薄层Al2O3,MgO或ZnO,讨论了不同包覆方法和实验条件对染料敏化太阳能电池性能的影响。研究表明,无论是原位包覆还是浸泡包覆,都可以在TiO2光阳极表面均匀的形成一层厚度约为1～2nm的氧化物包覆层,抑制了TiO2光阳极中的光生电子与氧化态染料和氧化态电解质的复合,从而导致光电压都有明显增大。特别是浸泡包覆不仅可以提高光电压,而且在较大的TiO2浆料粒径、合适的前驱体溶液浓度下,还可以增加光电流,导致光电转换效率明显增加。     

Sn3O4/光导纤维复合结构的制备及其光催化性能

传统光催化是光照射半导体催化剂时经表面光电耦合产生的载流子对有机污染物降解。这种外通光光催化模式使得光的利用率低、催化剂易失效、回收利用困难、难以实现连续水处理,制约了其在环保中的应用。本研究提出利用光的波导传输与界面耦合原理,通过在非晶光导纤维表面组装四氧化三锡纳米片,实现光的收集、传输及向纳米晶中注入,和内通光模式的光催化,从根本上解决上述问题。实验证明了四氧化三锡/光导纤维具有增强的光催化性能。这一研究首次提出光催化为目的非相干光波导传输和内通光光催化,拓宽了光波导理论并提出新的光催化反应机制,具有重要理论价值和巨大的工业应用前景。     

Au修饰薄膜CdSe电极的界面动力学行为的研究

研究了Au修饰的薄膜CdSe电极在多硫溶液中的瞬态光电流行为,测量了界面异相电荷转移,表面电荷复合及光腐蚀反应速度常数K_F,K_R及K_c。结合了光电子能谱(XPS)及扫描电镜(SEM)表面分析,对三种不同Au量修饰的薄膜CdSe电极进行界面动力学行为的分析。     

cdSe_xTe_(1-x)薄膜电极光溶解性能的研究

用循环伏安法对半导体Cdse_xTe_(1-x)薄膜电池的光溶解性能进行了研究。在1mol/L KCl溶液中测量光溶解产物的阴极还原特性,考察了在多硫化钠,多硫化钾及铁氰化钾溶液中的光腐蚀行为。用此方法还研究了薄膜电极表面的光刻蚀过程和pH的影响,并用X射线光电子能谱分析光刻进行不同时间后,电极表面发生的变化。     

修饰的薄膜CdSe电极／Fe（CN）6^4—溶液界面的电荷转移

本文研究了硬脂酸二茂铁酯L-B膜修饰的薄膜Cdse电极的光诱发界面多相电荷转移过程。通过测量异相电荷转移反应速度常数K_(et),进一步分析了修饰的薄膜CdSe电极光电化学过程的可能反应速度控制步。分析表明界面的电荷转移是反应的速度控制步。薄膜CdSe电极可以通过选择电活性修饰分子和溶液中氧化还原离子来进一步提高和改善其光电化学性能。     

薄膜CdSe及CdSexTe1—x电极的光电子能谱研究

用X射线光电子能谱(XPS)研究了不同含氧气氛中烧结的薄膜CdSe及Cdse_xTe_(1-x)电极表面,以及薄膜与Ti底基之间的界面。研究中发现,二种薄膜电极的表面形成了CdO,SeO_2及TeO_2氧化物,与薄膜接触的Ti底基表面上形成了TiO_2。用俄歇电子能谱(AES)对在电极表面及Ti表面所生成的氧化层分别进行了深度分析。结果表明,各种氧化物形成的程度有很大的不同,氧化层厚度也存在差异。对影响薄膜电极的光电性能的因素进行了讨论。     

Evaluation of sub-micrometer parylene C films as an insulation layer using electrochemical impedance spectroscopy

We investigated the insulation performance of sub-micrometer parylene C films over time using electrochemical impedance spectroscopy (EIS). For this, interdigitated electrodes were fabricated and completely encapsulated with parylene C in thicknesses of 50, 100, 200, and 500 nm. The EIS was measured in phosphate buffered saline (PBS) solution under an accelerated aging condition at 90 °C over 45 days. To analyze the EIS data, the equivalent circuit models of coating at different stages of coating degradation were used and the lumped circuit parameters of the best fitted equivalent circuit model were extracted by curve fitting. The analysis of impedance using the equivalent circuit model and the FTIR measurements suggest that sub-micrometer parylene C coatings exhibited delamination resulting from water diffusion from the top surface as soon as being immersed in PBS solution, although the degree of delamination varied depending on the film thickness. The penetration of water through sub-micrometers thick parylene C films can occur as quickly as the film is in contact with solution, unlike for thicker coatings in several micrometers where water diffusion would be saturated before water reaches the bottom surface of the coating.     

Homogeneous Co3O4 film electrode with enhanced oxygen evolution electrocatalysis via surface reduction

Homogeneous NaBH_4-reduced Co_O_4 thin film electrodes with enhanced oxygen evolution electrocatalysis were obtained via a controlled-synthesis route.Firstly CoOx colloids were synthesized via ethylene glycol solvothermal method and cast on conductive glass substrates.The oxygen evolution reaction(OER) electrocatalysis of these asprepared Co_3O_4 thin films were then significantly enhanced via a simple surface reduction by NaBH_4 solution.The OER catalytic performance of the NaBH_4-reduced thin films was strongly dependent on the NaBH_4 concentration.The use of NaBH_4-reduced thin film electrodes for OER in alkaline solution supported higher current density and consequently negative shifts of the onset potential compared to that of the pristine.The optimal B_(12.5,20)-Co_3O_4 thin films exhibited excellent OER catalytic performances:At the current density of 10 mA·cm~(-2),a low overpotential of 365 mV and a small Tafel slope of 59.0 mV·dec~(-1) were observed.In addition,these B_(12.5,20)-Co_3O_4 thin film electrodes possessed good stability that can well recover its OER performance in a 24-h chronoamperometric stability test.     

Electrochemical solar cells with polypyrrole-coated CdSe sintered electrodes

A thin layer of polypyrrole was formed on sintered CdSe electrodes. The photoelectrochemical properties of bare CdSe and P-Py/CdSe electrodes were studied in electrolyte with the redox couple [K₃Fe(CN)₆]. The results were explained by assuming that a p-n junction is formed on CdSe electrodes with polypyrrole working as a p-type semiconductor.     

Improved performance of dense TiO2/CdSe coupled thin films by low temperature process

Dense TiO₂ and TiO₂/CdSe coupled nanocrystalline thin films were synthesized onto ITO coated glass substrate by chemical route at relatively low temperature (≤100 °C). TiO₂ films were nanocrystalline and crystallinity disappears after CdSe deposition as evidenced by X-ray powder diffraction. Surface morphology and physical appearance of films were studied from SEM and actual photo-images, reveals dense nature of TiO₂ (10-12 nm spherical grains, faint violet) and CdSe (80-90 nm spherical grains, deep brown), respectively. Presence of two absorption edges in UV spectra implies existence of separate phases rather than composite formation. TiO₂ film was found to have higher water contact angle (71°) than TiO₂/CdSe (61°) and CdSe (56°). I-V and stability tests of photo-electrochemical cells were performed with TiO₂ and TiO₂/CdSe film electrodes (under light of illumination intensity 80 mW/cm²) in lithium iodide as an electrolyte using two-electrode system.     

Nanocomposite p‐n Junction Polycarbazole CdSe/TiO2 Thin Films on ITO via Electrochemical Crosslinking

The fabrication and characterization of a hybrid polymer p‐n junction‐type thin film via electropolymerization of NPs and a precursor polymer is described. Blends of TiO₂ NPs, CdSe NCs, Cbz‐COOH, and PVK were utilized to enable electrochemical deposition on ITO glass substrates. Spectroscopic, microscopic, and wetting measurements confirmed thin film fabrication. CV yielded a CPN nanocomposite with electropolymerized (i.e., crosslinked) carbazole units embedding CdSe NCs. Absorption and emission measurements confirmed a charge transfer mechanism between the crosslinked carbazole and the NCs resulting in a p‐n junction‐type thin film on ITO; with the observed quenching of CdSe NC emission. Several possible applications of such thin films are also discussed.

     

Facile solution growth of vertically aligned ZnO nanorods sensitized with aqueous CdS and CdSe quantum dots for photovoltaic applications

Vertically aligned single crystalline ZnO nanorod arrays, approximately 3 μm in length and 50-450 nm in diameter are grown by a simple solution approach on a Zn foil substrate. CdS and CdSe colloidal quantum dots are assembled onto ZnO nanorods array using water-soluble nanocrystals capped as-synthesized with a short-chain bifuncional linker thioglycolic acid. The solar cells co-sensitized with both CdS and CdSe quantum dots demonstrate superior efficiency compared with the cells using only one type of quantum dots. A thin Al2O3 layer deposited prior to quantum dot anchoring successfully acts as a barrier inhibiting electron recombination at the Zn/ZnO/electrolyte interface, resulting in power conversion efficiency of approximately 1% with an improved fill factor of 0.55. The in situ growth of ZnO nanorod arrays in a solution containing CdSe quantum dots provides better contact between two materials resulting in enhanced open circuit voltage.