Stoichiometric water splitting into H2 and O2 using a mixture of two different photocatalysts and an IO3-/I- shuttle redox mediator under visible light irradiation

The stoichiometric splitting of water into H2 and O2 (H2/O2 = 2) under visible light irradiation (lambda > 420 nm) took place for the first time using a mixture of Pt-WO3 and Pt-SrTiO3 (Cr-Ta-doped) photocatalysts and an IO3-/I- shuttle redox mediator.     

Photocatalytic overall water splitting under visible light by TaON and WO3 with an IO3-/I- shuttle redox mediator

Photocatalytic water splitting into H2 and O2 under visible-light irradiation (lambda > 420 nm) is demonstrated using the oxynitride Pt-TaON for H2 evolution and a Pt-WO3 catalyst for O2 evolution in an IO3-/I- shuttle redox-mediated system.     

基于镧和铬共掺杂钛酸锶产氢光催化剂构建Z机制全分解水体系（英文）

光催化剂的晶体结构、电子结构、表面结构等都会对自身性质产生决定性的作用,因此认识和理解光催化材料自身结构和光催化性能之间的内在联系有助于设计合成更高效的光催化剂以及光催化复合体系.本文通过聚合络合法和溶胶凝胶水热法分别制备了镧和铬共掺杂的光催化剂,标记为和在碘化钠或甲醇作为牺牲试剂的产氢反应中,担载Pt的样品显示了光催化活性,而担载Pt的样品活性很低,甚至无活性.我们将这两种材料分别作为产氢光催化剂与三氧化钨耦合构建Z机制全分解水体系.研究发现,只有体系观察到了氢气和氧气的产生.在第一个10 h的循环反应中,产生的摩尔比为3.7,明显高于水分解为2的化学计量比.这是因为在反应起始时加入的是Na I,质子还原产氢反应占据了主导.随着氢气的不断产生,部分I-被氧化成了IO_3-,而IO_3-的存在就可以驱动氧气的产生,由于溶液中氧化还原电的共存就可以持续驱动氢气和氧气的同时生成.为了测试体系的稳定性,我们将前面产生的气体完全抽空后又进行第二次10 h的循环反应,总共进行三次循环反应.在第一次循环过程中氢气、氧气生成速率分别为9.1和2.4mmol h~(–1),第二次循环其速率分别为9.9和3.7mmol h~(–1),第三次循环速率分别达到10.4和4.9mmol h~(–1).此外,通过三次循环后摩尔比为2.1,接近水分解的化学计量比.结合紫外可见漫反射光谱和Mott-Schottky曲线可以确定两种样品的能带位置.从能带位置示意图可知,两种样品都具有足够负的导带电势还原质子产氢以及足够正的价带电势氧化水产氧.需要指出的是样品的导带电势比样品的导带电势更负,这意味着前者的导带电势更有利于还原质子产氢.霍尔效应测试的结果表明,两种样品均显示出n型半导体的特征,此外样品显示出比样品更快的载流子迁移率以及更高的载流子浓度.因此,两种样品不同的导带位置以及不同的载流子迁移率和载流子浓度很可能是造成两者光催化性能具有显著差异的主要原因.     

Cr2O3-Rh/Ga2O3光催化分解水的时间分辨红外光谱研究

研究半导体光催化分解水反应中光生电荷动力学和助催化剂的作用对理解其反应机理至关重要.一般来说,助催化剂不仅可以促进半导体/助催化剂界面处的光生电荷高效分离,而且可以作为反应活性中心来直接催化表面氧化或还原反应.Cr₂O₃-Rh是一种重要的产氢助催化剂,通过担载Cr₂O₃-Rh助催化剂来提高光催化分解水的策略被应用到许多光催化分解水体系中.已有研究发现,Rh/Cr₂O₃核壳结构助催化剂的产氢活性位仍然在Rh纳米粒子表面,而Cr₂O₃壳层阻止O2到达Rh核从而抑制生成水的逆反应.此外,在(Rh_2-yCr_yO₃)/(Ga_1-xZn_x)(N_1-xO_x)光催化剂中,CrO_x促进了从半导体光催化剂到活性位RhOx的电子转移.然而,Cr₂O₃-Rh助催化剂的作用本质(包括Cr₂O₃所起的作用)仍然是一个悬而未决的问题,特别是Cr₂O₃-Rh助催化剂的担载对半导体催化剂中光生电荷动力学影响的研究还非常少.本文采用原位光沉积的方法制备了Ga₂O₃、Rh/Ga₂O₃、Cr₂O₃/Ga₂O₃和Cr₂O₃-Rh/Ga₂O₃等一系列光催化剂;采用紫外可见漫反射光谱(UV-Vis DRS)、X射线光电子能谱(XPS)、CO吸附红外光谱和高分辨透射电镜(HRTEM)等表征手段研究了Cr₂O₃-Rh助催化剂的结构和形貌;采用时间分辨红外光谱(TR-MIR)研究了这些光催化剂在真空或者反应物(水汽或者氧气)存在条件下的光生电子的衰减动力学过程.UV-Vis DRS结果表明,Ga₂O₃的带隙基本上不受Rh或者Cr₂O₃-Rh助催化剂担载的影响.XPS结果表明,Cr₂O₃和Rh成功地担载在Ga₂O₃表面上.CO吸附红外和HRTEM结果表明,在Cr₂O₃-Rh助催化剂中Rh纳米粒子被Cr₂O₃部分覆盖.光生电子的衰减动力学研究结果显示,Ga₂O₃中光生电子很难直接参与质子还原反应,只有被Rh捕获后的电子才能高效地参与产氢反应;在水汽存在条件下Ga₂O₃、Rh/Ga₂O₃和Cr₂O₃-Rh/Ga₂O₃中光生电子的衰减速率随着它们光催化产氢活性的升高而增加;与Cr₂O₃/Ga₂O₃和Rh/Ga₂O₃相比,Cr₂O₃-Rh/Ga₂O₃中光生电子的初始吸光度和寿命均减小,说明Cr₂O₃对Rh/Ga₂O₃的结构修饰促进了电子从Ga₂O₃向Rh的转移过程,从而加速了质子还原反应.最后,基于这些结果提出了Cr₂O₃-Rh/Ga₂O₃光催化剂上的光催化分解水机理.本文的研究结果有利于更加深入地认识半导体光催化分解水反应机理,并为高效半导体光催化剂的合成提供一定的理论支持和指导.     

Photophysical and photocatalytic properties of SrTiO3 doped with Cr cations on different sites

Usually, SrTiO3 monodoped with Cr cations at the Ti4+ site hardly shows visible light photocatalytic activity. Revealing the origin of this issue is important for us to find an alternative approach to make SrTiO3 active under visible light irradiation. In this paper, two Cr-doped SrTiO3-(Sr0.95Cr0.05)TiO3 and Sr(Ti0.95Cr0.05)O3-were synthesized by a conventional solid-state reaction method, and their photophysical and photocatalytic properties were studied comparatively. It was found that both (Sr0.95Cr0.05)TiO3 and Sr(Ti0.95Cr0.05)O3 showed considerable absorption to visible light. However, their photocatalytic activities for H2 evolution from aqueous methanol solution under visible light irradiation were significantly different: the H2 evolution rate over (Sr0.95Cr0.05)TiO3 (approximately 21 micromol/h) was more than 100 times that over Sr(Ti0.95Cr0.05)O3 (approximately 0.2 micromol/h). X-ray photoelectron spectroscopy analysis results revealed that the Cr cations doped at the Sr2+ site were all trivalent state (Cr3+), while those doped at the Ti4+ site were mixed valent states (Cr3+ and Cr6+). The different photocatalytic activities of H2 evolution are supposed to closely relate to the different valent states of Cr doped at different sites (Sr2+ or Ti4+) in SrTiO3. Possible electronic structures of (Sr0.95Cr0.05)TiO3 and Sr(Ti0.95Cr0.05)O3 were proposed in relation to their photophysical and photocatalytic properties.     

Recent progress in the development of carbonate-intercalated Zn/Cr LDH as a novel photocatalyst for hydrogen evolution aimed at the utilization of solar light

A series of novel photocatalysts Zn/Cr LDH with different Zn/Cr molar ratios (2?:?1, 3?:?1, 4?:?1 and 2?:?1-CO(3)) were fabricated by a co-precipitation method and evaluated for photodecomposition of water using visible light irradiation. Various characterization methods were employed to investigate the structures, morphologies and photocatalytic properties. In comparison to Zn/Cr (2?:?1) LDH, Zn/Cr-CO(3) (2?:?1) LDH extends the absorption edges to the visible region and exhibits good photocatalytic activity, even without the assistance of co-catalysts. The visible light photocatalytic activity is ascribed to the charge transfer spectra of octahedral Cr ions in LDH. Zn/Cr-CO(3) LDH shows enhanced photocatalytic activities compared to Zn/Cr LDH as carbonate ions oxidise by holes to form carbonate radicals, inhibit the rapid recombination of e(-) and h(+) charge carriers and thereby suppress the backward reaction to some extent. This work provides a detailed understanding of the semiconductor properties of LDHs for photocatalytical hydrogen evolution.     

Photocatalytic hydrogen production from water over M-doped La2Ti2O7 (M = Cr, Fe) under visible light irradiation (lambda > 420 nm)

In the search for efficient photocatalysts working under visible light, we have investigated the effect of cation substitution on a layered perovskite, La2Ti2O7. Among various metal dopants, only Cr and Fe induced intense absorption of visible light (lambda > 400 nm), and only these catalysts produced H2 photocatalytically from water in the presence of methanol under visible light irradiation (lambda > 420 nm). The polymerized complex method was found to be more efficient for fabrication of the present catalysts producing a more homogeneous structure than the solid-state reaction. The characterization by XRD, UV-vis DRS, XPS, and XANES revealed that doped Cr and Fe were present in the Cr3+ and Fe3+ states substituting for Ti sites in the La2Ti2O7 lattice. The theoretical calculation indicated that the most significant feature in the electronic band structure of the metal-doped La2Ti2O7 was the formation of a partially filled 3d band in the band gap of La2Ti2O7, while the contribution of these dopants on the valence band was negligible. Excitation of electrons from this localized interband to the conduction band of La2Ti2O7 was responsible for visible light absorption and the H2 evolution from water under visible light.     

Highly efficient water splitting into H2 and O2 over lanthanum-doped NaTaO3 photocatalysts with high crystallinity and surface nanostructure

NiO-loaded NaTaO(3) doped with lanthanum showed a high photocatalytic activity for water splitting into H(2) and O(2) in a stoichiometric amount under UV irradiation. The photocatalytic activity of NiO-loaded NaTaO(3) doped with lanthanum was 9 times higher than that of nondoped NiO-loaded NaTaO(3). The maximum apparent quantum yield of the NiO/NaTaO(3):La photocatalyst was 56% at 270 nm. The factors affecting the highly efficient photocatalytic water splitting were examined by using various characterization techniques. Electron microscope observations revealed that the particle sizes of NaTaO(3):La crystals (0.1-0.7 microm) were smaller than that of the nondoped NaTaO(3) crystal (2-3 microm) and that the ordered surface nanostructure with many characteristic steps was created by the lanthanum doping. The small particle size with a high crystallinity was advantageous to an increase in the probability of the reaction of photogenerated electrons and holes with water molecules toward the recombination. Transmission electron microscope observations and extended X-ray absorption fine structure analyses indicated that NiO cocatalysts were loaded on the edge of the nanostep structure of NaTaO(3):La photocatalysts as ultrafine particles. The H(2) evolution proceeded on the ultrafine NiO particles loaded on the edge while the O(2) evolution occurred at the groove of the nanostep structure. Thus, the reaction sites for H(2) evolution were separated from those of O(2) evolution over the ordered nanostep structure. The small particle size and the ordered surface nanostep structure of the NiO/NaTaO(3):La photocatalyst powder contributed to the highly efficient water splitting into H(2) and O(2).     

全固态Z-Scheme光催化材料应用于二氧化碳还原和光催化分解水研究进展

由两种不同的半导体催化剂和电子传输介质建立的Z-Scheme光催化体系,通过在可见光照射下分别在两种半导体催化剂上进行氧化反应和还原反应,实现两步法光催化分解水和二氧化碳还原.相较于离子型Z-Scheme光催化体系,全固态Z-Scheme光催化体系具有适用范围广、无副反应、光源利用率高等特性,具有更加广阔的应用前景.在此,我们简述了Z-Scheme光催化体系的反应机理,综述了全固态Z-Scheme光催化体系在光催化分解水和光催化还原CO₂领域的应用,并对未来全固态Z-Scheme光催化体系的发展进行了展望.     

Y2O3/Ag3VO4复合可见光催化剂的制备及其光催化性能

以Na3VO4.12H2O,AgNO3和Y(NO3)3.6H2O为原料,采用浸渍法制备了Y2O3/Ag3VO4复合可见光催化剂,并用XRD,SEM,XPS,UV-Vis等测试手段表征了试样的结构和性能。结果显示,Y2 O3/Ag3VO4复合可见光催化剂为单斜结构,Y以Y2 O3的形式分散在Ag3VO4晶体的表面。UV-Vis测试结果表明,Y2O3/Ag3VO4较纯Ag3VO4吸收带边发生了红移,在可见光区的吸收增强;以金属卤灯(波长大于400 nm)为光源,研究了Y2O3/Ag3VO4催化剂对甲基橙(MO)的可见光催化降解性能。结果发现,Y2O3/Ag3VO4复合可见光催化剂的光催化活性较纯Ag3VO4均有大幅提高,其中Y掺杂量为4%时活性最高。     

Site-selected doping of upconversion luminescent Er3+ into SrTiO3 for visible-light-driven photocatalytic H2 or O2 evolution

A series of upconversion luminescent erbium-doped SrTiO(3) (ABO(3)-type) photocatalysts with different initial molar ratios of Sr/Ti have been prepared by a facile polymerized complex method. Er(3+) ions, which were gradually transferred from the A to the B site with increasing Sr/Ti, enabled the absorption of visible light and the generation of high-energy excited states populated by upconversion processes. The local internal fields arising from the dipole moments of the distorted BO(6) octahedra promoted energy transfer from the high-energy excited states of Er(3+) with B-site occupancy to the host SrTiO(3) and thus enhanced the band-to-band transition of the host SrTiO(3). Consequently, the erbium-doped SrTiO(3) species with B-site occupancy showed higher photocatalytic activity than those with A-site occupancy for visible-light-driven H(2) or O(2) evolution in the presence of the corresponding sacrificial reagents. The results generally suggest that the introduction of upconversion luminescent agents into host semiconductors is a promising approach to simultaneously harnessing low-energy photons and maintaining redox ability for photocatalytic H(2) and O(2) evolution and that the site occupancy of doped elements in ABO(3)-type perovskite oxides greatly determines the photocatalytic activity.     

Photocatalyst Materials for Water Splitting

Various photocatalyst materials developed by the group of the present author are described. Alkali and alkaline earth tantalates have arisen as a new group of photocatalyst materials for splitting of water into H₂ and O₂ under ultraviolet irradiation. They showed activities even without co-catalysts such as Pt, being different from titanate photocatalysts. When NiO co-catalysts were loaded on the tantalate photocatalysts, the photocatalytic activities were markedly increased. Among the tantalates, NiO/NaTaO₃ doped with La showed the highest activity. BiVO₄, AgNO₃, and TiO₂ co-doped with Cr and Sb photocatalysts showed high activities for O₂ evolution in the presence of a sacrificial reagent (Ag⁺) under visible light irradiation ( > 420 nm). Pt/SrTiO₃ co-doped with Cr and Sb or Ta, Pt/NaInS₂, and Pt/AgInZn₇S₉ photocatalysts showed high activities for H₂ evolution from aqueous solutions containing reducing reagents under visible light irradiation. Furthermore, Cu- or Ni-doped ZnS photocatalysts showed H₂ evolution activities even without co-catalysts such as Pt.     

Visible-light-sensitive photocatalytic reaction on chromium-containing mesoporous silica: selective partial oxidation of propane with molecular oxygen

The photocatalytic reactivities of chromium-containing mesoporous silica molecular sieves (Cr-HMS) under visible light irradiation have been investigated. Cr-HMS involves tetrahedral chromium oxide (Cr-oxide) moieties which are highly dispersed and incorporated in the framework of molecular sieve with two terminal Cr=O groups. In the presence of propane with molecular oxygen, a partial oxidation proceeded under visible light irradiation to produce acetone and acrolein, with high selectivity, while a complete oxidation proceeded under UV light irradiation mainly to produce CO₂. The charge-transfer excited state of the tetrahedral Cr-oxide moieties plays a significant role in the photocatalytic reactions.     

利用Ni(OH)x助催化剂修饰提高g-C3N4纳米片/WO3纳米棒Z型纳米体系的可见光产氢活性的研究

光催化技术是目前解决能源和环境问题最具前景的手段之一,因此寻找高效光催化剂已成为光催化技术的研究热点.而在众多半导体催化剂中,廉价、环保且性能稳定的g-C3N4光催化剂在太阳光开发利用方面尤其引人关注.然而,由于g-C3N4的比表面小,活性位点少,以及光生电子/空穴对易复合等不足,严重导致其较低的光催化量子效率.因此,构造Z型体系和负载助催化剂等策略被广泛应用于提高g-C3N4光催化效率.在过去几年中,TiO2,Bi2WO6,WO3,Bi2MoO6,Ag3PO4和ZnO已经被成功证实可以与g-C3N4耦合而构造Z型光催化剂体系.其中,WO3/g-C3N4光催化剂体系,具有可见光活性的WO3导带中的光生电子和g-C3N4价带中的光生空穴容易实现Z型复合,从而保留了WO3的强氧化能力和g-C3N4的高还原能力,最终大幅度提高了整个体系的光催化活性.在g-C3N4的各种产氢助催化剂中,由于常用的Pt,Ag和Au等贵金属的高成本和低储量等问题严重限制了它们的实际应用,所以近年来各种非贵金属助催化剂(包括纳米碳,Ni,NiS,Ni(OH)2,WS2和MoS2等)得到了广泛的关注.我们采取廉价且丰富的Ni(OH)x助催化剂修饰g-C3N4/WO3耦合形成的Z型体系,开发出廉价高效的WO3/g-C3N4/Ni(OH)x三元产氢光催化体系.在该三元体系中,Ni(OH)x和WO3分别用于促进g-C3N4导带上光生电子和价带的光生空穴的分离及利用,从而使得高能的g-C3N4的光生电子在Ni(OH)x富集并应用于光催化产氢,而高能的WO3的光生空穴被应用于氧化牺牲剂三乙醇胺,最终实现了整个体系的高效光催化产氢活性及稳定性.我们通过直接焙烧钨酸铵和硫脲制备出WO3纳米棒/g-C3N4,并采用原位光沉积方法将Ni(OH)x纳米颗粒负载到WO3/g-C3N4上.随后,我们采取X射线衍射(XRD)、高分辨透射电子显微镜(HRTEM)、X射线光电子能谱分析(XPS)和比表面和孔径分布等表征手段来研究光催化剂的结构与形貌;采取紫外-可见漫反射表征方法来研究其光学性能;采取荧光光谱,阻抗和瞬态光电流曲线等表征手段来测试光催化剂的电荷分离性能;采取极化曲线和电子自旋共振谱等表征手段来证明光催化机理;采取光催化分解水产氢的性能测试来研究光催化剂的光催化活性与稳定性.XRD,HRTEM和XPS表征结果,表明WO3为有缺陷的正交晶系的晶体,直径为20–40纳米棒且均匀嵌入在g-C3N4纳米片上;Ni(OH)x为Ni(OH)2与Ni的混合物,其Ni(OH)2与Ni的摩尔比为97.4 : 2.6,Ni(OH)x粒径为20–50 nm且均匀分散在g-C3N4纳米片上,WO3/g-C3N4/Ni(OH)x催化剂界面之间结合牢固,其中WO3和Ni(OH)x均匀分布在g-C3N4上.紫外-可见漫反射表征结果表明,随着缺陷WO3的负载量增加,复合体系的吸收边与g-C3N4相比产生明显的红移,而加入Ni(OH)x助催化剂使得催化剂体系的颜色由黄变黑,明显地增加了可见光的吸收.荧光光谱,阻抗和瞬态光电流曲线结果表明,WO3和Ni(OH)x的加入能有效地促进光生电子/空穴的分离.极化曲线结果表明,掺入WO3和Ni(OH)x能降低g-C3N4的析氢过电位,从而提高光催化剂表面的产氢动力学.?O2?和?OH 电子自旋共振谱表明成功形成了WO3/g-C3N4 耦合Z 型体系.光催化分解水产氢的性能测试表明,20%WO3/g-C3N4/4.8%Ni(OH)x产氢效率最高(576 μmol/(g?h)),分别是g-C3N4/4.8%Ni(OH)x,20%WO3/g-C3N4和纯g-C3N4的5.7,10.8和230倍.上述结果充分证明,Ni(OH)x助催化剂修饰和g-C3N4/WO3 Z型异质结产生了极好的协同效应,最终实现了三元体系的极高的光催化产氢活性.     

K1.9Na0.1Ta2O6·2H2O的形貌可控合成及光催化性能

钽酸盐光催化材料往往具有较高的光催化活性.近年报道的钽酸盐光催化剂主要采用传统高温固相法制备,该方法不可避免地导致高温烧结,使合成的钽酸盐颗粒较大,比表面积较小,而且该方法具有不可克服的晶体转变、结晶度差、分解、挥发和纯度低等缺点,使制备的光催化剂活性较低.而纳米材料由于粒径小,提高了电子和空穴的扩散速度,大大降低了电子和空穴在材料内的复合几率,从而使光催化材料活性大幅提高.此外,粒径减小也使表面原子迅速增多,减小了光的漫反射,同时也使光吸收不易达到饱和,有利于提高光吸收效率.因此,制备纳米材料是提高半导体光催化剂活性的有效手段.目前,采用湿化学的溶液合成方法能在较低温度下获得粒度小且均匀、计量比准确的光催化剂粉末,但是合成钽酸盐光催化剂的水溶性钽前体即乙醇钽(或氯化钽)价格昂贵,而且对潮湿极端敏感易水解,使产物纯度降低,不适合工业化生产.近年来,尽管有文献报道以Ta2O5为原料利用水热、溶胶-凝胶和共沉淀等方法制备钽酸盐,但其合成条件苛刻,合成步骤复杂,合成周期较长,耗能大,产物产量较低且不均匀,很难实现产物的形貌控制来筛选出适合光催化反应的材料.目前关于纳米钽酸盐光催化材料形貌控制方面的研究鲜有报道,主要是由于Ta2O5极难溶解,很难实现液相合成.因此,纳米钽酸盐光催化材料的可控制备是研究的难点.我们发展了熔盐-水热制备钽酸盐新方法,实现了K1.9Na0.1Ta2O6·2H2O的可控制备.利用熔盐法制备一种可溶性钽酸盐前驱体,再通过水热法在液相进一步反应制得纳米钽酸盐光催化材料K1.9Na0.1Ta2O6·2H2O,通过控制反应条件实现了纳米钽酸盐K1.9Na0.1Ta2O6·2H2O的形貌调控,得到了纳米球、微球、去顶八面体形貌和类似榴莲形貌等不同形貌,而利用其它制备方法很难控制钽酸盐的形貌.另外,研究了制备材料吸附和光催化降解罗丹明B的性能,发现该材料光催化活性与形貌直接相关.表征结果表明,制备样品的X射线衍射(XRD)谱图尖锐,结晶较好,其各衍射峰位置均与K2Ta2O6一致,为纯相烧绿石结构,属于立方晶系,空间群为Fd3m.通过分析合成材料的元素组成及含量,确定K：Na：Ta比例近似为1.9：0.1：2.为了进一步研究属于烧绿石型化合物K1.9Na0.1Ta2O6·2H2O的结构,对不同形貌材料进行了红外光谱测试,所有样品在450–1000 cm–1的谱峰可归属于(K, Na)–O和Ta–O键的振动,3300 cm–1左右为晶体结构中水的羟基伸缩振动峰,1720 cm–1左右是晶体结构中水的弯曲振动峰.可以看出,不同形貌材料的红外谱图吸收带宽度和位置十分相似,只存在小的偏移和变化,进一步表明不同形貌的材料具有相似的晶体结构,与XRD结果一致.差热-热重分析确定了结构中所含结晶水数量近似为2.光催化性能测试结果表明,具有纳米球形貌的材料比表面积较大,因而光催化活性最高.     

Photocatalytic water splitting using modified GaN:ZnO solid solution under visible light: long-time operation and regeneration of activity

Overall water splitting using GaN:ZnO solid solution photocatalyst modified with Rh(2-y)Cr(y)O(3) nanoparticles as H(2) evolution cocatalysts under visible light (400 < λ < 500 nm) was examined with respect to long-term durability and regeneration of photocatalytic activity. The rate of visible light water splitting remained unchanged for 3 months (2160 h), producing H(2) and O(2) continuously at a stoichiometric amount. After 6 months of operation, a 50% loss of the initial activity occurred. Regeneration treatment of deactivated catalysts was attempted by reloading the Rh(2-y)Cr(y)O(3) cocatalyst. The degree of activity regeneration depended on the reloading amount. Up to 80% of the initial activity for H(2) evolution could be recovered under optimal treatment conditions. It was also found that deactivation of GaN:ZnO was suppressed to some extent by prior coloading of an O(2) evolution cocatalyst, which helped to suppress oxidative decomposition of GaN:ZnO by valence band holes, thereby improving the durability.     

利用地球上丰富的炭黑和NiS_2双助催化剂修饰提高CdS纳米片体系的可见光产氢活性(英文)

光催化产氢技术是目前解决能源和环境问题的最有潜力的方法之一,因此制备安全高效的光催化剂已成为目前的研究热点.在目前研究的各种光催化剂中,CdS光催化剂因为具有较窄的带隙(2.4 eV)和合适的导带位置,所以在可见光催化产氢领域受到广泛关注.然而,光生电子/空穴对易复合和光腐蚀作用极大地限制了CdS光催化剂的放大应用.因此,人们采用众多改性策略以提高CdS光催化剂的可见光产氢活性,其中构建CdS纳米结构和负载助催化剂被认为是最有效的方式.构建CdS纳米结构既可以缩短载流子的迁移路径,也可以减少CdS晶体中的缺陷.很多不同纳米结构的CdS光催化剂已经被开发,例如纳米线、纳米颗粒和纳米棒等.因为制备过程极为复杂繁琐,所以CdS纳米片的研究鲜见报道.本文采用乙酸鎘和硫脲为原材料,通过简单的溶剂热法合成了CdS纳米片.在CdS的各类助催化剂中,由于常用的Pt,Ag和Au等贵金属的高成本和低储量等问题严重限制了它们的实际应用,所以近年来众多非贵金属助催化剂(例如MoS_2,WS2,NiS,NiO和WC等)得到了广泛关注.由于非贵金属助催化剂存在弱电导率和低功函数等问题,影响了对光生电子的收集和利用.纳米碳材料具有极高的电导率、强可见光吸收、有效的载流子分离和较多的反应位点等优点,因此组合纳米碳材料和非贵金属助催化剂被认为是一种有效的解决方案.本文首次采用炭黑和NiS_2作为双助催化剂改性CdS纳米片,通过简单的溶剂热/沉淀两步法成功合成了廉价高效的CdS/CB/NiS_2三元光催化体系.光催化产氢性能测试表明,CdS-0.5%CB-1%NiS_2展现出最高的光催化效率(166.7μmol h~(-1)),分别是CdS NSs和CdS-1.0%NiS_2的5.16和1.87倍.X射线衍射、高分辨电子显微镜和X射线光电子能谱结果证实了CdS催化剂的片状结构,且炭黑和NiS_2成功负载在CdS纳米片表面.紫外-可见漫反射结果表明,随着炭黑和NiS_2的负载,复合催化剂的吸收边缘产生明显的红移,且对可见光的吸收增强.荧光光谱、阻抗和瞬态光电流曲线测试结果证明,炭黑和NiS_2的加入可以有效地促进光生电子/空穴对分离.极化曲线结果表明,加入炭黑和NiS_2可以降低CdS的产氢过电势,因此加速表面产氢动力学.总之,炭黑和NiS_2之间显著的协同效应极大地提高了可见光吸收,促进光生电子/空穴对分离,加速表面产氢动力学,最终得到了三元光催化体系极高的光催化产氢活性.     

Cr2O3/C@TiO2核壳型复合材料的设计合成及其光催化产氢性能

随着社会经济的快速发展,能源危机和环境污染问题成为世界各国关注的焦点.通过光催化剂将太阳能用于污染物降解、分解水产氢、CO2还原及有机物合成等领域,是解决上述问题的理想途径.过渡金属氧化物TiO2因其稳定性高、催化活性好、制备简单等优点,被认为是最理想的光催化材料.然而,TiO2带隙较宽、光响应范围窄、光量子效率低等缺点限制了其实际应用.将碳或Cr2O3与TiO2结合形成复合结构已被证明可以有效提升其光催化性能.另一方面,金属离子的掺杂可以有效提高氧化钛的可见光响应.本文利用具有高比表面积的金属有机骨架材料MIL-101(Cr)纳米材料作为模板、镉源和碳源,首先在MIL-101(Cr)表面可控生长TiO2纳米颗粒,获得MIL-101(Cr)@TiO2复合结构;然后在氮气保护下碳化形成Cr2O3/C@TiO2核壳型复合材料.碳化后,制备的复合材料具有模板的八面体形貌和高比表面积,MIL-101(Cr)中的Cr元素一部分会形成Cr2O3,一部分会掺杂到TiO2中,使得TiO2的吸收边红移.此外,Cr2O3/C@TiO2中的C有利于光的吸收和载流子的分离.这种独特的纳米结构赋予Cr2O3/C@TiO2复合材料优异的光催化性能.在300 W氙灯照射下,该复合材料光解水产氢的速率为446μmol h?1 g?1,约为纯TiO2的4倍.在可见光照射下,Cr2O3/C@TiO2分解水产氢的速率为25.5μmol h?1 g?1.将获得的粉体催化剂制备成光电极发现,Cr2O3/C@TiO2在全幅光照射下的光电流密度在0.4 V(vs.Ag/AgCl)下达到2.3 mA/cm2,约为纯TiO2的3.5倍.Cr2O3/C@TiO2光催化产氢活性的提高一方面是由于Cr掺杂到TiO2中使得其具有可见光响应,另一方面MIL-101碳化获得的Cr2O3/C有效促进了光生载流子的分离.     

Cr2O3/C@TiO2核壳型复合材料的设计合成及其光催化产氢性能

随着社会经济的快速发展,能源危机和环境污染问题成为世界各国关注的焦点.通过光催化剂将太阳能用于污染物降解、分解水产氢、CO2还原及有机物合成等领域,是解决上述问题的理想途径.过渡金属氧化物TiO2因其稳定性高、催化活性好、制备简单等优点,被认为是最理想的光催化材料.然而,TiO2带隙较宽、光响应范围窄、光量子效率低等缺点限制了其实际应用.将碳或Cr2O3与TiO2结合形成复合结构已被证明可以有效提升其光催化性能.另一方面,金属离子的掺杂可以有效提高氧化钛的可见光响应.本文利用具有高比表面积的金属有机骨架材料MIL-101(Cr)纳米材料作为模板、镉源和碳源,首先在MIL-101(Cr)表面可控生长TiO2纳米颗粒,获得MIL-101(Cr)@TiO2复合结构;然后在氮气保护下碳化形成Cr2O3/C@TiO2核壳型复合材料.碳化后,制备的复合材料具有模板的八面体形貌和高比表面积,MIL-101(Cr)中的Cr元素一部分会形成Cr2O3,一部分会掺杂到TiO2中,使得TiO2的吸收边红移.此外,Cr2O3/C@TiO2中的C有利于光的吸收和载流子的分离.这种独特的纳米结构赋予Cr2O3/C@TiO2复合材料优异的光催化性能.在300 W氙灯照射下,该复合材料光解水产氢的速率为446μmol h?1 g?1,约为纯TiO2的4倍.在可见光照射下,Cr2O3/C@TiO2分解水产氢的速率为25.5μmol h?1 g?1.将获得的粉体催化剂制备成光电极发现,Cr2O3/C@TiO2在全幅光照射下的光电流密度在0.4 V(vs.Ag/AgCl)下达到2.3 mA/cm2,约为纯TiO2的3.5倍.Cr2O3/C@TiO2光催化产氢活性的提高一方面是由于Cr掺杂到TiO2中使得其具有可见光响应,另一方面MIL-101碳化获得的Cr2O3/C有效促进了光生载流子的分离.     

可见光化的半导体光催化剂

光解水制氢能否实用化取决于太阳光的有效利用率, 研究开发可见光化的光催化剂成为当前光催化剂研究中的重要课题.本文介绍了利用 光解水制氢的反应机理,综述了近年来半导体光催化剂在利用可见光方面的研究进展,重点描述了这些光催化剂的结构,并对该领域今后的研究方向进行了展望.