A carbon-rich g-C3N4 with promoted charge separation for highly efficient photocatalytic degradation of amoxicillin

A novel carbon-rich g-C₃N₄ nanosheets with large surface area was prepared by facile thermal polymerization method using urea and 1,3,5-cyclohexanetriol. Plenty of carbon-rich functional groups were introduced into the surface layers of g-C₃N₄, which constructed the built-in electric field (BIEF) and resulted in improved charge separation; therefore, the carbon-rich g-C₃N₄ displayed superior photocatalytic activity for amoxicillin degradation under solar light. The contaminant degradation mechanism was proposed based on radical quenching experiments, intermediates analysis and density functional theory (DFT) calculation. Moreover, the reusing experiments showed the high stability of the material, and the amoxicillin degradation under various water matrix parameters indicated its high applicability on pollutants treatment, all of which demonstrated its high engineering application potentials.     

新颖CdMoO4/g-C3N4复合材料的制备及其可见光增强的电荷分离和光催化活性（英文）

半导体光催化技术因其能够完全矿化和降解废水以及废气中的各种有机和无机污染物而受到越来越多研究者关注.尽管TiO2作为光催化剂显示了良好的应用前景,但其只对紫外光响应,该部分能量大约仅占太阳光谱的5%,从而限制了其实际应用.因此,开发新型可见光响应光催化剂成为光催化领域的研究焦点之一.石墨相氮化碳(g-C3N4)作为一种光催化材料,由于具有良好的热和化学稳定性以及可见光响应而备受关注.然而,单纯的g-C3N4由于光生电荷载流子易复合,光催化效果并不理想.为进一步提高g-C3N4的光催化活性,构建g-C3N4基异质结复合光催化材料被认为是增强g-C3N4光生电子-空穴分离效率的有效方法.CdMoO4作为一种光催化材料,与g-C3N4匹配的能带有利于光生电子-空穴的分离,从而提高g-C3N4的光催化活性.本文通过便利的原位沉淀-煅烧过程,制备了新颖的CdMoO4/g-C3N4异质复合光催化材料.复合材料的晶相构成、形貌、表面化学组分和光学特性等通过相应的分析测试手段进行表征.光催化活性通过可见光下催化降解罗丹明B水溶液来评价.结果显示,将CdMoO4沉积在g-C3N4表面形成复合材料可明显提高光催化活性,且当CdMoO4含量为4.8 wt%时达到最佳的光催化活性.这种显著增强的光催化活性可能是由于CdMoO4/g-C3N4复合物能够有效地传输和分离光生电荷载流子,从而抑制了光生电子-空穴的复合.电化学阻抗、瞬态光电流和稳定荧光光谱测试结果证实,通过CdMoO4与g-C3N4复合可有效增强电荷分离效率.此外,活性物捕获实验表明,在光催化过程中空穴(h+)和超氧自由基(?O2?)是主要活性物种.根据莫托-肖特基实验并结合紫外-可见漫反射吸收光谱,得到了单纯g-C3N4和CdMoO4的能带结构,提出了形成的II型异质结有助于增强光催化活性的机理.     

SrTiO3/BiOI异质结构:界面电荷分离、增强光催化活性和反应机理（英文）

异质结构光催化剂为实现高效的电荷分离,提高光催化性能提供了一种有效的途径.虽然宽禁带和窄禁带光催化剂已经得到了广泛的研究,但它们在接触界面上的电荷分离和转移规律尚未完全揭示.本文采用简便的方法成功地制备了一种新型SrTiO3/BiOI(STB)异质结构光催化剂.该光催化剂中的异质结构可以将光吸收扩展到可见光范围,从而在可见光照射下获得较高的光催化NO去除性能.实验和理论证据表明,BiOI光生电子可以通过预成型的电子传递通道直接转移到SrTiO3表面.XRD和XPS结果表明,SrTO3/BiOI复合材料已成功制备.SEM和TEM图像显示了SrTiO3,BiOI和STB样品的形貌.能量色散X射线(EDX)元素图清楚地表明SrTiO3均匀分布在BiOI纳米片表面,证实BiOI与SrTiO3形成了界面.高分辨率XPS表明,电子从BiOI中Bi和I原子转移到STB化合物中SrTO3的Sr和Ti原子.采用DFT进一步确定了BiOI与SrTiO3相互作用的机制.电子局域函数(ELF)表明,STB的接触界面存在共价相互作用.SrTiO3和BiOI之间生成的共价键导致局域化超额电子(e-ex)的积累.在可见光照射下,界面内的电子交换增强,从而提高反应物活化和ROS生成的效率.采用自制的连续流反应体系,研究了在可见光照射下制备的样品对NO去除的光催化性能.与SrTiO3和BiOI相比,STB具有显著增强的可见光光催化活性,去除率为59.0%.UV-vis DRS显示,STB异质结的光吸收扩展到可见光范围.SrTiO3具有可见光活性,这归因于EPR所描述的氧空位的存在.随后计算态密度(DOS),发现氧空位可以形成缺陷能级,降低激发电子所需的光能.利用ESR光谱发现,STB上的ESR信号强度都要强得多,说明STB异质结具有较好的氧化能力,也说明光生载流子可以通过电子传递通道被有效地分离.原位红外光谱表明,在SrTiO3上,NO主要转化为NO2.STB的加速电荷分离和转移特性,促进活性氧的生成,从而进一步有效地将有毒中间体NO2转化为目标产物.设计并制备的SrTiO3/BiOI异质结光催化剂在可见光辐照下净化空气中NO的效率提高,同时抑制了有毒中间体的生成.通过实验和理论相结合的方法揭示了在两种材料的接触界面上建立的电子传递通道.来自BiOI的光生电子可以通过预先形成的电子传递通道直接转移到SrTiO3表面,从而促进了ROS的生成,所以整体的NO纯化效率和对有毒中间体的抑制作用提高.综上,本文提出了一种简单、新颖的促进空气污染物高效安全净化的策略.     

NiFe2O4/g-C3N4 heterojunction composite with enhanced visible-light photocatalytic activity

Spinel structure nickel ferrite (NiFe₂O₄) doped graphitic carbon nitride (g-C₃N₄) photocatalyst NiFe₂O₄/g-C₃N₄ was synthesized by the coprecipitation route to enhance the photocatalytic activity for the visible-light driven degradation of methyl orange. The NiFe₂O₄ doping content is responsible for the microstructure and photocatalytic activity of NiFe₂O₄/g-C₃N₄ samples. Compared with pure NiFe₂O₄ and g-C₃N₄, the 2-NiFe₂O₄/g-C₃N₄ composite with NiFe₂O₄ doping of 2.0 wt% exhibited excellent photocatalytic activity and superior stability after five runs for degrading methyl orange under visible light irradiation. The catalytic activity of 2-NiFe₂O₄/g-C₃N₄ sample produced using the coprecipitation route was higher than those of conventional 2-NiFe₂O₄/g-C₃N₄ bulks prepared by the impregnation approach. The prepared samples for the photocatalytic degradation of methyl orange followed pseudo-first-order reaction kinetics. It’s ascribed to the synergistic effect between NiFe₂O₄ and g-C₃N₄, which can inhibit the recombination of photoexcited electron-hole pairs, accelerate photoproduced charges separation, and enhance the visible light absorption.     

Novel PtPd alloy nanoparticle-decorated g-C3N4 nanosheets with enhanced photocatalytic activity for H2 evolution under visible light irradiation

PtPd bimetallic alloy nanoparticle (NP)-modified graphitic carbon nitride (g-C₃N₄) nanosheet photocatalysts were synthesized via chemical deposition precipitation. Characterization of the photocatalytic H₂ evolution of the g-C₃N₄ nanosheets shows that it was significantly enhanced when PtPd alloy NPs were introduced as a co-catalyst. The 0.2 wt% PtPd/g-C₃N₄ composite photocatalyst gave a maximum H₂ production rate of 1600.8 μmol g^–1 h^–1. Furthermore, when K₂HPO₄ was added to the reaction system, the H₂ production rate increased to 2885.0 μmol g^–1 h^–1. The PtPd/g-C₃N₄ photocatalyst showed satisfactory photocatalytic stability and was able to maintain most of its photocatalytic activity after four experimental photocatalytic cycles. In addition, a possible mechanism for the enhanced photocatalytic activity was proposed and verified by various photoelectric techniques. These results demonstrate that the synergistic effect between PtPd and g-C₃N₄ helps to greatly improve the photocatalytic activity of the composite photocatalyst.     

Fabrication of niobium doped titanate nanoflakes with enhanced visible-light-driven photocatalytic activity for efficient ibuprofen degradation

In this study, a novel class of niobium (Nb) doped titanate nanoflakes (TNFs) are fabricated through a one-step hydrothermal method. Nb doping affects the curving of titanate nanosheet, leading to the formation of nanoflake structure. In addition, Nb⁵⁺ filled in the interlayers of [TiO₆] alters the light adsorption property of pristine titanate. The band gap of Nb-TNFs is narrowed to 2.85 eV, while neat titanate nanotubes (TNTs) is 3.4 eV. The enhanced visible light adsorption significantly enhances the visible-light-driven activity of Nb-TNFs for ibuprofen (IBP) degradation. The pseudo-first order kinetics constant for Nb-TNFs is calculated to be 1.04 h^?1, while no obvious removal is observed for TNTs. Photo-generated holes (h⁺) and hydroxyl radicals (OH) are responsible for IBP degradation. The photocatalytic activity of Nb-TNFs depends on pH condition, and the optimal pH value is found to be 5. In addition, Nb-TNFs exhibited superior photo-stability during the reuse cycles. The results demonstrated Nb-TNFs are very promising in photocatalytic water purification.     

原位合成具有高可见光催化活性的C3N4/CdS纳米复合材料

以硫氰酸铵和氯化镉为原料,采用无模板混合高温煅烧法一步合成氮化碳/硫化镉纳米晶(C3N4/CdS)的复合半导体材料。采用X射线衍射、傅立叶变换红外光谱和透射电镜等技术对其结构和形貌进行了表征。以有机污染物罗丹明B (RhB)为模拟污染物对复合催化剂的可见光催化活性进行测试。结果表明, C3N4/CdS复合材料中CdS以六方相纳米晶的形式均匀分散; CdS的复合基本不改变C3N4主体结构及聚合度;与纯C3N4相比,复合材料在可见区的光吸收能力有所增强。合适的能带匹配有利于光生载流子的迁移,抑制了其复合速率。在可见光照射下,复合半导体能够更加快速的降解有机污染物,且保持很好的稳定性。     

原位合成具有高可见光催化活性的C3N4/CdS纳米复合材料

以硫氰酸铵和氯化镉为原料,采用无模板混合高温煅烧法一步合成氮化碳/硫化镉纳米晶(C3N4/CdS)的复合半导体材料。采用X射线衍射、傅立叶变换红外光谱和透射电镜等技术对其结构和形貌进行了表征。以有机污染物罗丹明B (RhB)为模拟污染物对复合催化剂的可见光催化活性进行测试。结果表明, C3N4/CdS复合材料中CdS以六方相纳米晶的形式均匀分散; CdS的复合基本不改变C3N4主体结构及聚合度;与纯C3N4相比,复合材料在可见区的光吸收能力有所增强。合适的能带匹配有利于光生载流子的迁移,抑制了其复合速率。在可见光照射下,复合半导体能够更加快速的降解有机污染物,且保持很好的稳定性。     

2D/2D BiOBr/g-C3N4 S型异质结光催化性能

近年来,能源短缺和环境污染严重威胁人类的可持续发展.光催化技术具有绿色环保、成本低等优势,被认为是解决上述问题的最佳途径之一,其实用化的核心是开发高效可见光催化材料.石墨相氮化碳(g-C3N4)因其物理化学性质稳定、无毒、廉价及能带适宜等特点,广泛应用于光催化领域.然而,光生载流子易复合、比表面积小等问题不利于其实际应...     

Integrating non-precious-metal cocatalyst Ni3N with g-C3N4 for enhanced photocatalytic H2 production in water under visible-light irradiation

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.     

Highly enhanced visible-light photocatalytic hydrogen evolution on g-C3N4 decorated with vopc through π-π interaction

Photocatalytic H₂ evolution reactions on pristine graphitic carbon nitrides (g-C₃N₄), as a promising approach for converting solar energy to fuel, are attractive for tackling global energy concerns but still suffer from low efficiencies. In this article, we report a tractable approach to modifying g-C₃N₄ with vanadyl phthalocyanine (VOPc/CN) for efficient visible-light-driven hydrogen production. A non-covalent VOPc/CN hybrid photocatalyst formed via π-π stacking interactions between the two components, as confirmed by analysis of UV-vis absorption spectra. The VOPc/CN hybrid photocatalyst shows excellent visible-light-driven photocatalytic performance and good stability. Under optimal conditions, the corresponding H₂ evolution rate is nearly 6 times higher than that of pure g-C₃N₄. The role of VOPc in promoting hydrogen evolution activity was to extend the visible light absorption range and prevent the recombination of photoexcited electron-hole pairs effectively. It is expected that this facile modification method could be a new inspiration for the rational design and exploration of g-C₃N₄-based hybrid systems with strong light absorption and high-efficiency carrier separation.     

In-situ polymerization for PPy/g-C3N4 composites with enhanced visible light photocatalytic performance

Polypyrrole-modified graphitic carbon nitride composites (PPy/g-C₃N₄) are fabricated using an in-situ polymerization method to improve the visible light photocatalytic activity of g-C₃N₄. The PPy/g-C₃N₄ is applied to the photocatalytic degradation of methylene blue (MB) under visible light irradiation. Various characterization techniques are employed to investigate the relationship between the structural properties and photoactivities of the as-prepared composites. Results show that the specific surface area of the PPy/g-C₃N₄ composites increases upon assembly of the amorphous PPy nanoparticles on the g-C₃N₄ surface. Owing to the strong conductivity, the PPy can be used as a transition channel for electrons to move onto the g-C₃N₄ surface, thus inhibiting the recombination of photogenerated carriers of g-C₃N₄ and improving the photocatalytic performance. The elevated light adsorption of PPy/g-C₃N₄ composites is attributed to the strong absorption coefficient of PPy. The composite containing 0.75 wt% PPy exhibits a photocatalytic efficiency that is 3 times higher than that of g-C₃N₄ in 2 h. Moreover, the degradation kinetics follow a pseudo-first-order model. A detailed photocatalytic mechanism is proposed with ·OH and ·O₂^? radicals as the main reactive species. The present work provides new insights into the mechanistic understanding of PPy in PPy/g-C₃N₄ composites for environmental applications.     

新型BiOI/g-C3N4纳米片复合光催化剂的制备及其可见光催化活性增强

近年来, 石墨型氮化碳(g-C3N4)作为一种n型半导体光催化剂材料, 由于具有较好的热稳定性和化学稳定性, 同时具有可调的带隙结构和优异的表面性质而备受人们关注. 然而, 传统的g-C3N4块体材料存在比表面积小、光响应范围窄和光生载流子易复合等缺陷, 制约着其光催化活性的进一步提高. 因此, 人们开发了多种技术对块体状g-C3N4材料进行改性,其中构建基于g-C3N4纳米薄片的异质结复合光催化材料被认为是强化g-C3N4载流子分离效率, 进而提高其可见光催化活性的重要手段. BiOI作为一种窄带隙的p型半导体光催化剂, 具有强的可见光吸收能力和较高的光催化活性, 同时它与g-C3N4纳米薄片具有能级匹配的带隙结构. 因此, 基于以上两种半导体材料的特性, 构建新型的BiOI/g-C3N4纳米片复合光催化剂材料不仅能够有效提高g-C3N4的可见光利用率, 而且还可以在n型g-C3N4和p型BiOI界面间形成内建电场, 极大促进光生电子-空穴对的分离与迁移效率.为此, 本文通过简单的一步溶剂热法在g-C3N4纳米薄片表面原位生长BiOI纳米片材料, 成功制备了新型的BiOI/g-C3N4纳米片复合光催化剂. 利用X射线衍射仪(XRD), 场发射扫描电子显微镜(SEM)、透射电子显微镜(TEM)、紫外-可见漫反射光谱和瞬态光电流响应谱对所合成复合光催化剂的晶体结构、微观形貌、光吸收性能和电荷分离性能进行了表征测试. XRD, SEM和TEM结果显示, 结晶完好的BiOI呈小片状均匀分散在g-C3N4纳米薄片表面; 紫外漫反射光谱表明, 纳米片复合材料的吸光性能较g-C3N4薄片有显著提升; 瞬态光电流测试证明, 复合材料较单一材料有更好的电荷分离与迁移性能.在可见光催化降解RhB的测试中, BiOI/g-C3N4纳米片复合光催化剂显示出了优异的催化活性和稳定性, 其光降解活性分别为纯BiOI和g-C3N4的34.89和1.72倍; 自由基捕获实验发现, 反应过程中的主要活性物种为超氧自由基(·O2-), 即光生电子主导整个降解反应的发生. 由此可见, 强的可见光吸收能力和g-C3N4与BiOI界面处形成的内建电场协同促进了g-C3N4纳米薄片的电荷分离, 进而显著提高了该复合材料的可见光催化降解活性. 此外, 本文初步验证了在BiOI/g-C3N4纳米片复合光催化体系内光生电荷是依据"双向转移"机制进行分离和迁移的, 而非"Z型转移"机制.     

Cascaded electron transition in CuWO_4/CdS/CDs heterostructure accelerating charge separation towards enhanced photocatalytic activity

CuWO_4,as an n-type oxide semiconductor with a bandgap of 2.2 eV,has stimulated enormous interest as a potential broad-spectrum-active photocatalyst for environmental pollution remediations.However,rapid charge recombination greatly hinders its practical applications.Herein,we present a cascaded electron transition pathway in a ternary heterostructure consisting of CdS quantum dots,carbon dots(CDs) and CuWO_4 hollow spheres,which proves to greatly facilitate the photogenerated electron-hole separation,and eventually boosts the degradation efficiency of phenol and congo red by 100% and 46%compared to bare CuWO_4.The enhanced performance of the CuWO_4/CdS/CDs heterostructure mainly originates from the unidirectional electron migration from CdS to CuWO_4 and then to the organics through CDs.This work elucidates the electron transfer kinetics in multi-phase system and provides a new design paradigm for optimizing the properties of CuWO_4 based photocatalysts.     

原位制备具有增强光催化活性的S型Bi2Se3/g-C3N4光催化剂

光催化氧化是一种应用前景良好的环境治理技术.与絮凝、物理吸附和化学氧化等常见的方法相比,光催化氧化具有环境友好、氧化完全、方便和廉价等优势.特别是可见光光催化氧化,可利用太阳能中占比最高的可见光,在应用中更具优势.因而,探索可见光响应性能优异的光催化剂一直是光催化氧化领域的一个重要研究内容.硒化铋(Bi₂Se₃)是一种带隙(带隙宽度在0.3~1.3 e V)非常窄的半导体,能吸收全部波长范围的可见光和近红外光.此外,Bi₂Se₃还具有独特的金属表面态,其表面具有良好的导电性.这些特性使其在可见光光催化氧化领域具有很大的应用潜力.然而,由于Bi₂Se₃价带位置高,氧化能力很弱,其价带上的空穴在光催化反应中难以被消耗,导致空穴大量累积,并迅速与光生电子复合,大幅降低了Bi₂Se₃的光催化性能.因此,一直以来,Bi₂Se₃很少被用于光催化反应.如何充分利用Bi₂Se₃的光响应优势,制备出性能优异的光催化剂,仍是具有挑战性和吸引力的研究方向.本文采用预先制备的Bi2O3/g-C₃N₄复合物作为前驱体,通过原位转化的方法,将前驱体置于热的Se蒸汽中,使前驱体上的Bi2O3与Se蒸汽反应,完全转化为Bi₂Se₃纳米颗粒,从而制得Bi₂Se₃/g-C₃N₄复合光催化剂(Bi₂Se₃含量约为4 wt%).透射电镜结果表明,所形成的Bi₂Se₃纳米颗粒较均匀地分布在g-C₃N₄表面.表面功函数分析发现,Bi₂Se₃与g-C₃N₄结合后,它们的费米能级分别由原来的-0.55和-0.18 e V变为平衡时的-0.22 e V,可形成指向g-C₃N₄的内建电场,有利于形成梯型(S型)异质结.在此基础上,能级位移、荧光分析、结构计算和反应自由基测试等结果表明,Bi₂Se₃和g-C₃N₄之间形成了S型异质结.在可见光光催化降解苯酚的实验中,所制备的Bi₂Se₃/g-C₃N₄复合物的光催化活性明显优于单一的Bi₂Se₃和g-C₃N₄.结合比表面、孔结构、光吸收和荧光等对比分析,认为Bi₂Se₃/g-C₃N₄的这种S型异质结构在其光催化活性增强中起到了关键作用.在光照条件下,其g-C₃N₄导带中光生电子向Bi₂Se₃的价带迁移,并与光生空穴复合,从而使Bi₂Se₃导带上可保留更多的高活性光生电子参与光催化反应,由此Bi₂Se₃/g-C₃N₄的光催化活性增强.循环性能测试和光还原实验结果表明,所制备的Bi₂Se₃/g-C₃N₄复合光催化剂具有良好的稳定性.本文工作为高可见光吸收的光催化剂制备和性能增强提供了新途径和新视野.     

Z-scheme TiO2/g-C3N4 composites prepared by hydrothermal assisted thermal polymerization with enhanced visible light photocatalytic activity

Melamine was added to the precursor of TiO₂, then TiO₂ prepared by hydrothermal, while melamine was modified. Subsequently, a series of Z-scheme TiO₂/g-C₃N₄ heterojunction composites were successfully synthesized by simple calcination. The morphology and structure of samples were characterized by XRD, FT-IR, UV–vis DRS, SEM, TEM, PL and BET. The photocatalytic activity of these samples has been investigated by degradation of Rhodamine B (RhB), and results indicated that photocatalytic activity of the as-prepared samples was greatly influenced by the content of titanium tetrabutoxide in precursors and the hydrothermal time. The degradation rate of TiO₂/g-C₃N₄-1 to RhB was the best, which was 5.05-fold of pure TiO₂ (19.61%) and 2.25-fold of bulk g-C₃N₄ (44.06%), respectively. The trapping experiment results showed that ^·O₂^? and h⁺ were main active species during degradation of RhB. The photocatalytic activity of the sample did not decrease significantly after 4 cycles. The unique Z-scheme heterojunction between TiO₂ and g-C₃N₄ improved photocatalytic activity of the samples under visible light.

     

Enhanced photocatalytic H2 production over dual-cocatalyst-modified g-C3N4 heterojunctions

Ag nanoparticles (NPs) were deposited on the surface of g-C₃N₄ (CN) by an in situ calcination method. NiS was successfully loaded onto the composites by a hydrothermal method. The results showed that the 10 wt%-NiS/1.0 wt%-Ag/CN composite exhibits excellent photocatalytic H₂ generation performance under solar-light irradiation. An H₂ production rate of 9.728 mmol·g^?1·h^?1 was achieved, which is 10.82-, 3.45-, and 2.77-times higher than those of pure g-C₃N₄, 10 wt%-NiS/CN, and 1.0 wt%-Ag/CN composites, respectively. This enhanced photocatalytic H₂ generation can be ascribed to the co-decoration of Ag and NiS on the surface of g-C₃N₄, which efficiently improves light harvesting capacity, photogenerated charge carrier separation, and photocatalytic H₂ production kinetics. Thus, this study demonstrates an effective strategy for constructing excellent g-C₃N₄-related composite photocatalysts for H₂ production by using different co-catalysts.     

利用硫化铋纳米颗粒增强类石墨相氮化碳的光生载流子分离效率和光催化活性（英文）

二氧化钛,氧化锌,磷酸铋等传统的紫外光响应光催化剂虽然具有良好的光催化性能,但是对太阳能利用率很低(紫外光只占太阳光能量的4%左右).近年来,类石墨相氮化碳(g-C3N4)受到了广泛的关注.g-C3N4的带隙约2.7 eV,它只能吸收460nm以下的光,对太阳能的利用率依然比较低.构筑异质结是一种有效的提高光催化活性的方法.BiOCl/g-C3N4,TiO2/g-C3N4, Bi2MoO6/g-C3N4, Al2O3/g-C3N4, Ag3PO4/g-C3N4等异质结光催化剂曾被广泛的报道.硫化铋是属于正交晶系的窄带隙半导体,它的带隙约1.3–1.7 e V.由于其独特的电子结构和光学特性,硫化铋在光催化,光检测器和医药成像等领域有着广泛的应用.另外,硫化铋还具有优异的光热转换性能,在光热癌症治疗领域有显著的效果.微波辅助法,水热法,惰性气体下高温煅烧法等都曾被用来合成g-C3N4/Bi2S3异质结光催化剂.不同的文献也提出了不同的催化机理.如何使用更简单环保的方法来合成g-C3N4/Bi2S3异质结光催化剂?电子和空穴的转移路径是怎样的?本文利用简单的低温方法合成了硫化铋,利用超声法得到了g-C3N4/Bi2S3异质结光催化剂,分析了其微观形貌,结构,并探讨了光催化的反应机理和提高光催化性能的因素.X射线衍射,傅里叶变换红外光谱, X射线光电子能谱和透射电子显微镜的结果表明,硫化铋纳米颗粒被成功地引入到g-C3N4中.使用亚甲基蓝为分子探针研究了所制材料在模拟太阳光下的光催化活性.结果发现, CN-BiS-2表现出最佳的光催化活性,是g-C3N4的2.05倍,是Bi2S3的4.42倍.利用液相色谱二级质谱联用分析了亚甲基蓝的降解路径.硫化铋的引入拓展了复合材料的吸收边,使其向可见光区红移,且在整个可见光区的光吸收能力都有明显的增强.光电流的增强和交流阻抗谱圆弧半径的减小,表明光生载流子的迁移与分离速率得到了增强.自由基捕获试验表明,最主要的活性物种是光生空穴,次之是羟基自由基和超氧自由基.在CN-Bi S-2样品中羟基自由基和超氧自由基的电子顺磁共振信号都比g-C3N4有明显的增强,表明复合样品中能够产生更多的羟基自由基和超氧自由基.基于光电流,交流阻抗,荧光光谱,自由基捕获和电子顺磁共振的结果,我们提出了高能电子由硫化铋转移到g-C3N4,同时空穴由g-C3N4转移到硫化铋的电子空穴转移机制.此外,红外热成像的结果表明, g-C3N4/Bi2S3异质结材料具有更强的光热转换能力,从而有利于加速光生载流子分离.     

C-I共掺杂多孔g-C3N4光催化分解水制氢

氢气是一种可替代传统燃料的理想清洁能源,利用光催化技术分解水制氢是制取氢气的有效途径之一.无机半导体光催化材料具有较高的活性和稳定性,且原料丰富,易加工改性.目前针对光催化技术的应用,大量的研究工作都集中在开发可见光响应光催化剂,以提高对可见光的利用率.同时,非金属聚合物半导体因其特殊的光电性质,在光催化应用研究中越来越受到关注,如庚嗪基微孔聚合物(HMP)和共价三嗪基骨架(CTF).石墨相碳化氮(g-C3N4)是一种典型非金属二维聚合物半导体,被认为是一种非常有价值的光催化材料.然而,其较低的光生电子的传输效率限制了其实际应用,因此诸多研究对g-C3N4的物理化学结构进行优化,如半导体耦合、共聚合、纳米结构设计和掺杂.非金属掺杂是一种有效的方法,由于原子电负性差异引起的电荷分离可有效改善载流子传输效率,且保持半导体的非金属性质.通过O,B,P和S等掺杂可以扩大可见光响应范围,并调节能带位置以改善光催化活性.除了常见的单一非金属掺杂,金属和非金属元素或多非金属元素共掺杂的办法同样可提高g-C3N4的光催化性能.本工作通过两步法对双氰胺、尿素和碘化1-乙基-3-甲基咪唑的混合物直接热聚合,合成C-I共掺杂的多孔g-C3N4,其在可见光照射下表现出较高的产氢活性和稳定性.采用X射线衍射(XRD)、X射线光电子能谱(XPS)、荧光光谱(PL)和电化学实验等方法对多孔掺杂g-C3N4结构进行详细表征和分析.在助催化剂Pt和电子牺牲剂(三乙醇胺)存在的条件下,采用可见光(>400 nm)照射分解水产氢的方法评价其光催化活性.结果表明,后热处理和碘离子液掺杂对g-C3N4材料的结构和性能具有较大影响.C-I共掺杂和后热处理使催化剂产物颗粒尺寸减小,形成多孔片层状紧密堆积,比表面积和孔隙率显著增加,吸收带边发生蓝移.后热处理使样品层间距减小,聚合度增加,有利于电荷传输,C-I共掺杂后出现更多的缺陷,但没有改变其层状堆积的特性.XPS结果表明,样品中碘元素以I-和I5+的形式存在,改性后催化剂C/N比明显增加,sp2芳环N含量增加,表面氨基含量降低,表明后热处理和C-I共掺杂没有改变多孔g-C3N4的基本骨架,共轭结构更加完善.PL和光电流结果表明,改性后样品的PL强度均显著降低,并且随着掺杂量的增加而逐渐降低,表明共掺杂可抑制光生电荷的复合.电化学测试结果表明,后热处理和C-I共掺杂的样品界面电荷转移电阻降低,导电率和电荷迁移率增加,从而有助于提高光催化性能.光解水产氢性能测试表明,后热处理和C-I共掺杂有利于催化剂产氢速率的提高,改性后CNIN0.2的产氢速率达168.2μmol/h,是纯氮化碳的9.8倍.经过多次循环测试,其产氢性能保持稳定而没有显著下降,表明其产氢稳定性较好.     

Preparation of Z-scheme WO3(H2O)0.333/Ag3PO4 composites with enhanced photocatalytic activity and durability

Ag₃PO₄ is widely used in the field of photocatalysis because of its unique activity. However, photocorrosion limits its practical application. Therefore, it is very urgent to find a solution to improve the light corrosion resistance of Ag₃PO₄. Herein, the Z-scheme WO₃(H₂O)_0.333/Ag₃PO₄ composites are successfully prepared through microwave hydrothermal and simple stirring. The WO₃(H₂O)_0.333/Ag₃PO₄ composites are characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV-Vis spectroscopy. In the degradation of organic pollutants, WO₃(H₂O)_0.333/Ag₃PO₄ composites exhibit excellent performance under visible light. This is mainly attributed to the synergy of WO₃(H₂O)_0.333 and Ag₃PO₄. Especially, the photocatalytic activity of 15%WO₃(H₂O)_0.333/Ag₃PO₄ is the highest, and the methylene blue can be completely degraded in 4 min. In addition, the stability of the composites is also greatly enhanced. After five cycles of testing, the photocatalytic activity of 15%WO₃(H₂O)_0.333/Ag₃PO₄ is not obviously decreased. However, the degradation efficiency of Ag₃PO₄ was only 20.2%. This indicates that adding WO₃(H₂O)_0.333 can significantly improve the photoetching resistance of Ag₃PO₄. Finally, Z-scheme photocatalytic mechanism is investigated.