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1.
采用水热法和多巴胺还原法制备了Bi OBr、Bi OBr/石墨烯和Au/Bi OBr/石墨烯光催化剂,并利用扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)、光致发光光谱(PL)和紫外-可见漫反射光谱(UV-vis DRS)等方法表征其形貌、相结构、光谱吸收性质以及组成结构。在可见光照射下,通过对水相中苯酚的降解,考察了Au/Bi OBr/石墨烯复合光催化剂活性。结果表明,由于量子效率的提高、带隙能的降低(2.25 e V)以及Au表面等离子体共振,复合光催化剂表现出比纯Bi OBr更高的光催化活性,Au/Bi OBr/石墨烯复合物在180 min内对苯酚降解率可达到64%。  相似文献   

2.
为提高太阳能转化效率, 高效响应可见光的光催化剂的研究十分必要. 本研究以硫化镉、氯化钯、醋酸镍和硫脲为原料, 利用水热法制备了NiS-PdS/CdS复合光催化剂. 通过X射线衍射(XRD)、紫外-可见光漫反射光谱(DRS)、透射电子显微镜(TEM)和光致发光(PL)光谱等手段对光催化剂进行了表征, 并在乳酸牺牲剂中对光解水制氢活性进行了测试. 结果表明: 助催化剂NiS 和PdS 能较好地分布在CdS 表面上, 形成共负载的NiS-PdS/CdS 光催化剂, 其可见光下的活性比CdS明显增强, 当NiS 和PdS 负载量分别在1.5%和0.41%(w)时, NiS-PdS/CdS获得最好活性, 最大产氢量达到6556 μmol·h-1, 是CdS活性的7倍, 是NiS/CdS的近3倍, 测得在λ=420 nm时的表观量子效率为47.5%. 助催化剂NiS 和PdS分别起到传递光生电子和光生空穴的作用,两者共负载相比于单独负载, 能使光生载流子的迁移和分离效率更高, 因此提高了光催化产氢活性.  相似文献   

3.
氢能是最具应用前景的清洁能源之一,利用太阳能作为驱动力光催化水分解制取氢气已被广泛研究.作为非金属半导体光催化剂, g-C_3N_4具有合适的能带结构(2.71 eV),良好的可见光捕获能力和物理化学稳定性,因而有一定的光催化产氢能力;但是它具有可见光吸收能力(470 nm)不够、光生电子空穴容易复合等缺点,使其光催化制氢能力受到了极大限制.通过助剂修饰可有效促进载流子分离,增加反应活性位点及加速产氢动力学.因此,本文采用双助剂改性以提高g-C_3N_4的光催化制氢性能.本文首先采用原位煅烧法将银纳米粒子(AgNPs)沉积在g-C_3N_4表面(Ag/g-C_3N_4),随后利用水热法成功地将硫化镍(NiS)负载在Ag/g-C_3N_4复合材料表面.XRD, FT-IR, XPS和TEM结果表明,通过原位煅烧和水热合成法可以成功地将Ag和NiS均匀、稳定沉积在g-C_3N_4表面,并且g-C_3N_4保持原有结构不变.紫外可见吸收光谱(UV-Vis)、瞬态光电流、阻抗(EIS)和光致发光谱(PL)分析表明, AgNPs和NiS的引入不仅改善了体系的光吸收范围和强度,而且显著提高了体系光生电子和空穴的产生、分离性能,有助于提高光子利用效率.其中三元样品的最高光电流可以达到2.94′10–7 A·cm~(–2),是纯g-C_3N_4的3.1倍.对系列光催化剂的分解水制氢性能测试发现(采用300 W氙灯作为光源,三乙醇胺作为牺牲剂), 10wt%-NiS/1.0wt%-Ag/CN样品具有最优异的光催化分解水制氢性能,产氢速率可达9.728 mmol·g–1·h–1,是纯g-C_3N_4的10.82倍,二元10wt%-NiS/CN的3.45倍, 1.0wt%-Ag/CN的2.77倍.三元样品反应前后的XRD特征峰位置没有发生变化,循环四次后样品仍具有83%的催化活性,证明其具有良好的制氢稳定性.10 wt%-NiS/1.0 wt%-Ag/CN样品在可见光下(λ 420 nm)的制氢量子效率为1.21%.三元体系光催化产氢性能增强的原因在于:(1)Ag纳米颗粒的局域表面等离子体效应使得三元体系的光捕获能力得到提高;(2)Ag NPs和NiS负载在g-C_3N_4上共同促进了光生电子空穴的产生和分离;(3)Ag NPs和Ni S作为优良的析氢助催化剂沉积在g-C_3N_4表面上可以有效地提高产氢动力学.本文构建的NiS/Ag/g-C_3N_4复合体系为g-C_3N_4基复合光催化剂的设计及制备提供了新的思路.  相似文献   

4.
采用一步煅烧法使类石墨烯碳氮化合物(g-C_3N_4)和磷化镍(Ni_2P)复合并对其光催化产氢性能进行研究.利用X射线粉末衍射、透射电镜、X射线光电子能谱、紫外可见光谱对该复合催化剂的组成、形貌等进行了表征.研究了不同含量的Ni_2P以及不同牺牲剂对g-C_3N_4/Ni_2P光催化性能的影响.与单独的g-C_3N_4相比,该复合催化剂的光催化产氢速率提高了13倍,可以达到165μmol g~(-1)·h~(-1).利用光电化学和光致发光光谱等技术对该复合光催化剂的光催化产氢机理进行研究,结果表明Ni_2P在高效分离光生载流子方面起了关键作用,并且g-C_3N_4和Ni_2P的复合产生了协同效应加速了电子-空穴对的分离,提高了光催化产氢性能.  相似文献   

5.
为了研究复合光催化剂在光催化中的制氢效率,采用水热法制备了Mo S2纳米片,然后通过水热法在Mo S2纳米片上负载了TiO_2纳米颗粒,形成了Mo S2/TiO_2异质结复合催化剂。采用冷场发射扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、紫外-可见吸收光谱(UV-Vis)、拉曼光谱(Raman),X射线光电子能谱(XPS)对材料的结构和光学性能表征并进行分析。通过光催化制氢测试对光催化剂进行评价,实验结果表明,在波长为365 nm的紫外光照射下,最高光催化制氢速率为1004μmol·h-1·g-1,对应的催化剂的Mo S2含量为30%,其催化速率远大于单一的Mo S2和TiO_2,表明Mo S2/TiO_2复合催化剂在紫外光照下能显著提高光催化产氢性能。基于Mo S2/TiO_2复合光催化剂优越的光催化产氢性能,本文对复合光催化剂的产氢机理做了研究和分析。  相似文献   

6.
利用半导体光催化剂(Cd S、g-C_3N_4、TiO_2等)产氢是将太阳能转换为氢能以满足未来能源需求的前瞻性策略之一。在众多光催化剂中,TiO_2因其合适的还原电位和出色的化学稳定性而备受关注。然而,TiO_2受光激发产生的电子和空穴容易发生猝灭而表现出有限的光催化性能。由于具备优异的导电性和稳定性,石墨烯可以作为一种有效的电子助剂加速光生电子的传输,进而提高TiO_2的产氢性能。但是,在光催化反应中,除了光生电子的快速转移外,石墨烯表面的界面产氢反应也非常重要。因此,有必要进一步优化石墨烯的微观结构(功能化石墨烯),以提高石墨烯基TiO_2光催化剂的产氢性能。通常,石墨烯的功能化是一个可以在石墨烯表面上引入产氢活性位点的有效策略。与非共价功能化(例如在石墨烯表面上加载Pt,MoSx和CoSx)相比,石墨烯的共价功能化可以通过化学反应将产氢活性位点与石墨烯表面的官能团相结合,并形成强相互作用,有利于界面的产氢反应。本文将开环和酯化反应制备的羧基功能化石墨烯(rGO-COOH)成功地通过超声辅助自组装法修饰TiO_2得到高活性的TiO_2/rGO-COOH光催化剂。傅立叶变换红外(FTIR)光谱显著增强的―COOH官能团特征峰、X射线光电子能谱(XPS)中的峰面积变化和热重(TG)曲线的质量变化证实了GO向rGOCOOH的成功转变。X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、XPS和紫外可见漫反射光谱(UV-Vis)等一系列表征可证明TiO_2/rGO-COOH光催化剂的成功合成。光催化产氢测试结果表明TiO_2/rGO-COOH样品表现出较高的产氢活性(254.2μmol·h~(-1)·g~(-1)·),分别是TiO_2/GO和TiO_2的2.06和4.48倍。光催化活性提高可归因于羧基功能化石墨烯中具有优异亲核性的羧基可以富集氢离子,并作为有效的产氢活性位点,显著地提高TiO_2的界面产氢反应速率。这项研究为我们在光催化产氢领域中开发高活性石墨烯负载的光催化剂提供了新的思路。  相似文献   

7.
太阳能光催化分解水制氢是太阳能制氢的最佳途径之一.选择CdS为敏化剂,制备了可见光响应的CdS复合钛酸纳米管光催化剂.以所制备的光催化剂在不同模拟有机污染物中的光催化产氢活性进行研究,对有机物浓度、pH值等反应参数进行了考察,并对其产氢机理进行了分析.研究发现各类有机物中,甲酸溶液中产氢量活性最高.分别考察了10%、2...  相似文献   

8.
光催化分解水产氢是利用太阳能解决当今能源危机和环境污染问题的理想策略.硫化镉光催化剂由于具有较窄的带隙、有效的光吸收能力、较负的导带位置和较强的还原能力等而受到广泛关注.然而,硫化镉光催化剂的光生电子-空穴复合速率高,导致其光催化活性比较低,因此在光催化领域的应用受到限制.为此,人们采取了很多方法来改善硫化镉光催化剂的光催化性能,例如加入助催化剂、构建异质结、表面修饰以及形成固溶体光催化剂等.合成固溶体光催化剂被认为是提高硫化镉光催化活性最具有发展前景的方法之一,固溶体光催化剂通过形成轨道杂化而表现出可控的带隙和带边位置.在固溶体光催化剂中,锌镉硫胶体量子点引起了很多关注.锌镉硫胶体量子点的颗粒尺寸较小,这就使得光生电子和空穴由催化剂内部转移到表面的距离较短,增大了载流子分离效率.另外,锌镉硫胶体量子点具有较负的导带位置、可调控的带隙、较好的水中分散性以及良好的光吸收等优点,因此锌镉硫胶体量子点从其他光催化剂中脱颖而出.本文分别采用热注法和传统共沉淀法制备了油溶性锌镉硫量子点和水溶性锌镉硫纳米颗粒.发现油溶性量子点亲水性能较差,几乎没有光催化活性,但油溶性量子点易通过配体交换过程转换成水溶性量子点,无机硫作为锌镉硫量子点的表面水溶性配体,可使量子点具有较好的亲水性.通过电化学测试、稳态荧光以及时间分辨荧光测试结果表明,相比于锌镉硫纳米颗粒,水溶性锌镉硫量子点具有更高的电子空穴分离效率.光催化产氢测试发现,在牺牲剂甘油存在的条件下,水溶性锌镉硫量子点的光催化产氢速率(1220μmol g^?1 h^?1)显著提高,约是锌镉硫纳米颗粒产氢速率的10倍.加入助催化剂Ni^2+后,锌镉硫量子点表现出最高的光催化产氢活性(2253μmol g^?1 h^?1),在420 nm灯的光照条件下,表观量子效率达到15.9%.光催化活性的增大主要归因于量子点较小的颗粒尺寸、表面无机硫配体以及助催化剂的添加,这些都有利于载流子的快速分离和转移,降低其复合,延长其寿命,并且加速了产氢动力学,因此提高了水溶性锌镉硫量子点的光催化产氢活性.  相似文献   

9.
采用共沉淀法制备了Cd0.53Zn0.47S固溶体光催化剂,以光还原沉积法负载Pt,水解正硅酸乙酯负载SiO2,得到了负载Pt的SiO2复合光催化剂SiO2/Pt-Cd0.53Zn0.47S,并研究了水解pH值对其催化活性的影响.通过X射线衍射(XRD)、比表面(BET)、荧光光谱(PL)、紫外-可见漫反射光谱(UV-Vis DRs)和扫描电镜(SEM)等测试技术对催化剂进行了表征.结果表明,SiO2复合光催化剂有效地抑制了Pt-Cd0.53Zn0.47S光催化过程中发生的光腐蚀和粒子团聚,促使光生电子和空穴分离,从而使可见光制氢催化剂活性和稳定性大大提高.  相似文献   

10.
采用共沉淀法制备了Cd0.53Zn0.47S固溶体光催化剂,以光还原沉积法负载Pt,水解正硅酸乙酯负载SiO2,得到了负载Pt的SiO2复合光催化剂SiO2/Pt-Cd0.53Zn0.47S,并研究了水解pH值对其催化活性的影响.通过X射线衍射(XRD)、比表面(BET)、荧光光谱(PL)、紫外-可见漫反射光谱(UV-Vis DRS)和扫描电镜(SEM)等测试技术对催化剂进行了表征.结果表明,SiO2复合光催化剂有效地抑制了Pt-Cd0.53Zn0.47S光催化过程中发生的光腐蚀和粒子团聚,促使光生电子和空穴分离,从而使可见光制氢催化剂活性和稳定性大大提高.  相似文献   

11.
Metal-organic frameworks (MOFs) have been shown to be an excellent platform in photocatalysis. However, to suppress electron–hole recombination, a Pt cocatalyst is usually inevitable, especially in photocatalytic H2 production, which greatly limits practical application. Herein, for the first time, monodisperse, small-size, and noble-metal-free transitional-metal phosphides (TMPs; for example, Ni2P, Ni12P5), are incorporated into a representative MOF, UiO-66-NH2, for photocatalytic H2 production. Compared with the parent MOF and their physical mixture, both TMPs@MOF composites display significantly improved H2 production rates. Thermodynamic and kinetic studies reveal that TMPs, behaving similar ability to Pt, greatly accelerate the linker-to-cluster charge transfer, promote charge separation, and reduce the activation energy of H2 production. Significantly, the results indicate that Pt is thermodynamically favorable, yet Ni2P is kinetically preferred for H2 production, accounting for the higher activity of Ni2P@UiO-66-NH2 than Pt@UiO-66-NH2.  相似文献   

12.
Solar light harvesting by photocatalytic H2 evolution from water could solve the problem of greenhouse gas emission from fossil fuels with alternative clean energy. However, the development of more efficient and robust catalytic systems remains a great challenge for the technological use on a large scale. Here we report the synthesis of a sol–gel prepared mesoporous graphitic carbon nitride (sg‐CN) combined with nickel phosphide (Ni2P) which acts as a superior co‐catalyst for efficient photocatalytic H2 evolution by visible light. This integrated system shows a much higher catalytic activity than the physical mixture of Ni2P and sg‐CN or metallic nickel on sg‐CN under similar conditions. Time‐resolved photoluminescence and electron paramagnetic resonance (EPR) spectroscopic studies revealed that the enhanced carrier transfer at the Ni2P–sg‐CN heterojunction is the prime source for improved activity.  相似文献   

13.
Photocatalytic H2 production via water splitting in a noble-metal-free photocatalytic system has attracted much attention in recent years. In this study, noble-metal-free Ni3N was used as an active cocatalyst to enhance the activity of g-C3N4 for photocatalytic H2 production under visible-light irradiation (λ > 420 nm). The characterization results indicated that Ni3N nanoparticles were successfully loaded onto the g-C3N4, which accelerated the separation and transfer of photogenerated electrons and resulted in enhanced photocatalytic H2 evolution under visible-light irradiation. The hydrogen evolution rate reached ~305.4 μmol h?1 g?1, which is about three times higher than that of pristine g-C3N4, and the apparent quantum yield (AQY) was ~0.45% at λ = 420. Furthermore, the Ni3N/g-C3N4 photocatalyst showed no obvious decrease in the hydrogen production rate, even after five cycles under visible-light irradiation. Finally, a possible photocatalytic hydrogen evolution mechanism for the Ni3N/g-C3N4 system is proposed.  相似文献   

14.
Photocatalytic water splitting coupled with the production of highly value-added organic chemicals is of significant importance, which represents a very promising pathway for transforming green solar energy into chemical energy. Herein, we report a composite photocatalyst CdIn2S4@MIL-53-SO3Ni1/2, which is highly efficient on prompting water splitting for the production of H2 in the reduction half-reaction and selective oxidation of organic molecules for the production of highly value-added organic chemicals in the oxidation half-reaction under visible light irradiation. The superior photocatalytic properties of the composite photocatalyst CdIn2S4@MIL-53-SO3Ni1/2 should be ascribed to coating suspended ion catalyst (SIC), consisting of redox-active NiII ions in the anionic pores of coordination network MIL-53-SO3, on the surface of photoactive CdIn2S4, which endows photogenerated electron-hole pairs separate more efficiently for high rate production of H2 and selective production of highly value-added organic products, demonstrating great potential for practical applications.  相似文献   

15.
The development of efficient photocatalytic H2-evolution materials requires both rapid electron transfer and an effective interfacial catalysis reaction for H2 production. In addition to the well-known noble metals, low-cost and earth-abundant non-noble metals can also act as electron-transfer mediators to modify photocatalysts. However, as almost all non-noble metals lack the interfacial catalytic active sites required for the H2-evolution reaction, the enhancement of the photocatalytic performance is limited. Therefore, the development of new interfacial active sites on metal-modified photocatalysts is of considerable importance. In this study, to enhance the photocatalytic evolution of H2 by Ni-modified TiO2, the formation of NiSx as interfacial active sites was promoted on the surface of Ni nanoparticles. Specifically, the co-modified TiO2/Ni-NiSx photocatalysts were prepared via a two-step process involving the photoinduced deposition of Ni on the TiO2 surface and the subsequent formation of NiSx on the Ni surface by a hydrothermal reaction method. It was found that the TiO2/Ni-NiSx photocatalysts exhibited enhanced photocatalytic H2-evolution activity. In particular, TiO2/Ni-NiSx(30%) showed the highest photocatalytic rate (223.74 μmol h?1), which was greater than those of TiO2, TiO2/Ni, and TiO2/NiSx by factors of 22.2, 8.0, and 2.2, respectively. The improved H2-evolution performance of TiO2/Ni-NiSx could be attributed to the excellent synergistic effect of Ni and NiSx, where Ni nanoparticles function as effective mediators to transfer electrons from the TiO2 surface and NiSx serves as interfacial active sites to capture H+ ions from solution and promote the interfacial H2-evolution reaction. The synergistic effect of the non-noble metal cocatalyst and the interfacial active sites may provide new insights for the design of highly efficient photocatalytic materials.  相似文献   

16.
As an environmentally friendly approach to generate H2, electrocatalytic water splitting has attracted worldwide interest. However, its broad employment has been inhibited by costly catalysts and low energy conversion efficiency, mainly due to the sluggish anodic half reaction, the O2 evolution reaction (OER), whose product O2 is not of significant value. Herein, we report an efficient strategy to replace OER with a thermodynamically more favorable reaction, the oxidation of 5‐hydroxymethylfurfural (HMF) to 2,5‐furandicarboxylic acid (FDCA), catalyzed by 3D Ni2P nanoparticle arrays on nickel foam (Ni2P NPA/NF). HMF is one of the primary dehydration intermediates of raw biomass and FDCA is of many industrial applications. As a bifunctional electrocatalyst, Ni2P NPA/NF is not only active for HMF oxidation but also competent for H2 evolution. In fact, a two‐electrode electrolyzer employing Ni2P NPA/NF for simultaneous H2 and FDCA production required a voltage at least 200 mV smaller compared with pure water splitting to achieve the same current density, as well as exhibiting robust stability and nearly unity Faradaic efficiencies.  相似文献   

17.
Photocatalytic water splitting to obtain hydrogen energy can transform low-density solar to high density, new and clean energy in a clean way, which is one of the ideal ways to solve the energy crisis and environmental pollution. In this paper, The CoxP/hollow porous C3N4 composite photocatalytic material was synthesized by simple methods. The photocatalytic hydrogen production rate of CoxP/hollow porous C3N4 reaches 1602 μmol g−1 h−1, which is 151 times of that of pure C3N4. The reasons for the high photocatalytic H2 evolution activity of CoxP/hollow porous C3N4 could be summarized as follows: (1) the hollow and porous structure of C3N4 shows higher light capture efficiency, larger specific surface area and more surface active sites. (2) metalloid CoxP loaded forms the Schottky contact with C3N4, which improves the photogenerated charges separation efficiency of C3N4, prolongs the photogenerated charges lifetime and improves the photocatalytic H2 evolution activity of C3N4. (3) The higher conductivity of metalloid CoxP and the lower overpotential of hydrogen production are other reasons for the higher activity of photocatalytic hydrogen production of CoxP/hollow porous C3N4. This work provides an important role for the design of efficient, stable, and efficient construction of photocatalysts for solar energy conversion.  相似文献   

18.
Water is the most sustainable source for H2 production, and the efficient electrocatalytic production of H2 from mixed water/acetonitrile solutions by using two new air-stable nickel(II) pincer complexes, [Ni(κ3-2,6-{Ph2PNR}2(NC5H3)Br2] (R=H I , Me II ) is reported. Hydrogen generation from H2O/CH3CN solutions is initiated at −2 V against Fc+/0, and bulk electrocatalysis studies showed that the catalyst functions with an excellent Faradaic efficiency and a turnover frequency of 160 s−1. A DFT computational investigation of the reduction behavior of I and II revealed a correlation of H2 formation with charge donation from electrons originating in a reduced ligand-localized orbital. As a result, these catalysts are proposed to proceed by a novel mechanism involving electron/proton transfer between a Ni0I species bonded to an anionic PN3P ligand (“L/Ni0I”) and a NiI-hydride (“Ni−H”). Furthermore, these catalysts are able to reduce phenol and acetic acid, more active proton sources, at lower potentials that correlate with the substrate pKa.  相似文献   

19.
Hydrogen peroxide (H2O2) has received increasing attention because it is not only a mild and environmentally friendly oxidant for organic synthesis and environmental remediation but also a promising new liquid fuel. The production of H2O2 by photocatalysis is a sustainable process, since it uses water and oxygen as the source materials and solar light as the energy. Encouraging processes have been developed in the last decade for the photocatalytic production of H2O2. In this Review we summarize research progress in the development of processes for the photocatalytic production of H2O2. After a brief introduction emphasizing the superiorities of the photocatalytic generation of H2O2, the basic principles of establishing an efficient photocatalytic system for generating H2O2 are discussed, highlighting the advanced photocatalysts used. This Review is concluded by a brief summary and outlook for future advances in this emerging research field.  相似文献   

20.
Photocatalytic hydrogen (H2) production represents a very promising but challenging contribution to a clean, sustainable and renewable energy system. The photocatalyst material plays a key role in photocatalytic H2 production, and it has proven difficult to obtain corrosion resistant, chemically stable, visible light harvesting and highly efficient photocatalysts, which have their band edges matching the O2 and H2 production levels. Nanoscience and nanotechnology are opening a new vista in the development of highly active, nanostructured photocatalysts with large surface areas for optimized light absorption, minimized distances (or times) for charge-carrier transport, and further favorable properties. Our focus here is on recently developed nanostructured photocatalysts. In particular, the particle size, chemical composition (including dopants), microstructure, crystal phase, morphology, surface modification, bandgap and flat-band potential of the nanophotocatalysts have shown a visible effect on photocatalytic H2 production rates, which may be further increased by adding sensitizers, cocatalysts or scavengers. Finally, potential directions required to push this research field a step further are highlighted.  相似文献   

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