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1.
黄艳  傅敏  贺涛 《物理化学学报》2015,31(6):1145-1152
用简单的超声分散法合成了具有可见光响应的类石墨氮化碳(g-C3N4)/BiVO4复合光催化剂. 采用X射线衍射(XRD), X射线光电子能谱(XPS), 扫描电子显微镜(SEM), 透射电子显微镜(TEM), 紫外-可见(UV-Vis)分光光谱, 傅里叶红外变换(FTIR)光谱, 荧光发射谱(PL)和光电流响应等技术对所制备催化剂进行相关表征. 通过可见光下(λ> 420 nm)光催化还原CO2的性能来评价样品的光催化活性, 发现不同复合比的催化剂中, 含40% (w) g-C3N4的复合催化剂表现出最高的光催化活性, 其催化活性分别为纯g-C3N4纳米片和纯BiVO4的催化活性的2倍和4倍.光催化活性增加的主要原因是g-C3N4和BiVO4之间形成了异质结, 且相互间能级匹配, 有利于光生电子和空穴的分离.  相似文献   

2.
随着工业技术的飞速发展,大量有机污染物被应用于生活的各个领域,由此带来了严重的环境问题。众所周知,半导体光催化技术是一种有效且环境友好的降解去除典型污染物的方法,而光催化剂在该技术的应用中起着关键作用。因此,在光催化污染物降解领域,人们已经尝试研究了各种半导体材料。其中石墨相氮化碳(g-C3N4)是近年来公认的“明星”材料之一。因其独特的二维层状结构和良好的可见光响应而引起了人们的极大兴趣。由于带隙较窄(~2.7 eV)、能带结构可调以及良好的物理化学稳定性,g-C3N4对太阳光谱的吸收可达450 nm,具有一定的可见光光催化性能。然而,g-C3N4在去除抗生素和染料方面的降解效率仍然存在不足,例如光生电荷的快速复合以及空穴的氧化能力弱等。为了优化这种有前景的光催化材料,人们尝试了多种方法来改善g-C3N4的电子能带结构,例如金属/非金属元素掺杂、形貌调控和官能团修饰等。最近,人们提出了由两种N型半导体光催化剂组成的梯形异质结理念,它可以利用半导体材料更正的价带和更负的导带。相关结果表明,构筑梯形异质结是提高g-C3N4光催化活性的最有效方法之一。因此,本文通过简单的原位溶剂热生长法制备了新型0D/2D Bi4V2O11/g-C3N4梯形异质结光催化剂。Bi4V2O11/g-C3N4复合材料对去除土霉素(OTC)和活性红染料展示出了优异的光催化活性。尤其是BVCN-50复合材料对OTC和活性红的降解效率高达74.1%和84.2%,该过程的主要活性物种为·O2-。大幅增强的光催化性能归因于Bi4V2O11和g-C3N4之间形成的梯形异质结保持了光催化体系的强氧化还原能力(Bi4V2O11的强氧化能力和g-C3N4的强还原能力),并促进了光生电荷的空间分离。此外,金属Bi0的表面等离子共振效应可以拓宽异质结系统的光吸收范围。此外,基于高效液相色谱-质谱联用(LC-MS)分析,我们研究了OTC降解过程中可能的中间体和降解路径。这项工作为设计和制备g-C3N4基梯形异质结用于抗生素和活性染料降解提供了一种新的策略。  相似文献   

3.
使用尿素、 红磷和氯化镍为原料, 通过一种简单的焙烧方法合成了Ni5P4/g-C3N4光催化剂. 该催化剂形成的异质结可以降低界面电阻, 有效抑制光生电子-空穴对复合率. 以罗丹明B模拟污染物进行降解测试, 发现3NPC的反应速率常数最高, 几乎是g-C3N4的7倍, 并具有最高的光催化产氢能力, 制氢速率高达1013.88 μmol·g-1·h-1, 明显高于g-C3N4(664.38 μmol·g-1·h-1).  相似文献   

4.
构建具有高效电荷迁移效率和丰富活性位点的异质结光催化体系是提升光芬顿反应速率的有效途径。本研究通过简单的水热法合成了2D/2D结构的α-Fe2O3/g-C3N4 S型异质结光芬顿催化剂,并使用X射线衍射仪技术(XRD)、透射电子显微镜(TEM)、傅立叶变换红外吸收光谱(FTIR)和紫外-可见吸收光谱(UV-Vis)等分析手段对α-Fe2O3/g-C3N4的晶体结构、微观结构、化学组分和光学性质进行了详细的表征。通过在可见光照射下降解四环素,评测了α-Fe2O3/g-C3N4的催化活性。结果表明,光催化反应与芬顿反应的协同作用使α-Fe2O3/g-C3N4 (1 : 1)展现出了优异的光芬顿催化活性:在可见光照射下,仅加入微量的双氧水便可辅助催化剂在20 min内对四环素的降解率达到78%,其降解速率分别是单一的α-Fe2O3和g-C3N4的3.5倍和5.8倍。α-Fe2O3/g-C3N4复合材料优异的催化活性得益于在2D/2D S型电荷迁移机制上构建的光芬顿催化体系。2D/2D S型异质结能够显著促进电子和空穴的传输与分离,并为催化剂提供较大的比表面积和丰富的活性位点,同时还能保持复合材料最佳的氧化还原能力。此外,光催化反应促进了Fe3+的还原,从而加速了芬顿反应中羟基自由基的产生。总之,本研究为构建高效、稳定的光芬顿催化体系提供了一条简单有效的途径。  相似文献   

5.
采用原位光沉积-煅烧法制得了Z型α-Fe2O3/g-C3N4异质结复合光催化剂。分别采用透射电子显微镜、X射线衍射、X射线光电子能谱、紫外可见漫反射光谱、荧光光谱以及电化学测试对样品进行了表征,并考察了可见光下光解水产氢活性。结果表明:当α-Fe2O3的负载量为2.9%时,α-Fe2O3/g-C3N4复合光催化剂具有最优的产氢催化活性,产氢速率高达1841.9μmol·g-1·h-1,约为g-C3N4的3.3倍。光催化性能的提高主要归因于3方面:(1)高温煅烧过程中α-Fe2O3的形成,有效促进了氮化碳片层的热剥离,增大了比表面积,从而为光催化反应提供了更多反应活性位;(2)超细α-Fe2O3颗粒(5~8 nm)高度均匀地分散在g-C3N4表面,并且与其紧密结合,形成了高质量的Z型异质结;(3)Z型异质结不仅有效抑制地了光生载流子的复合,同时极大地保留了g-C3N4导带电子的强还原性和α-Fe2O3价带空穴的强氧化性。  相似文献   

6.
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, ·O2-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.  相似文献   

7.
通过在尿素前驱体中添加单宁酸, 原位缩聚形成碳自掺杂石墨相氮化碳(g-C3N4). 利用X射线光电子能谱(XPS)、 场发射扫描电子显微镜(FESEM)、 X射线衍射(XRD)仪和同步热分析(TG-DSC)等方法对碳自掺杂 g-C3N4的形貌、 物相结构和能带价态组分进行表征分析, 结合紫外-可见吸收光谱(UV-Vis)和原位光微量热-荧光光谱联用仪获得碳自掺杂g-C3N4降解罗丹明B的原位热/动力学信息和三维荧光光谱信息, 探讨了光催化降解罗丹明B的微观机制. 结果表明, 单宁酸浓度≤10 mg/mL时, 碳会取代七嗪单元结构的氮原子形成g-C3N4骨架碳自掺杂; 单宁酸浓度≥ 20 mg/mL时, 碳以无定形形式沉积负载在g-C3N4表面上形成无定形碳自掺杂. 骨架碳自掺杂g-C3N4形成的π电子有效缩短了禁带宽度, 减小了光生电子-空穴复合几率, 比无定形C掺杂g-C3N4显示出更优异的光催化性能, 催化主要活性物种为h+和·O2-. 碳自掺杂g-C3N4光催化降解过程可分为光响应吸热、 降解污染物放热平衡过程和稳定放热3个过程. 其中骨架碳自掺杂g-C3N4(C/N摩尔比为0.844)在光照1000 s内, 三维荧光光谱检测的RhB降解率锐减, 光照1000 s后, 其RhB降解率为87.6%, 分别是原始g-C3N4和无定形碳自掺杂g-C3N4的3.13倍和1.95倍. 光照1000 s后, 光微量热计显示以矿化和降解非荧光发色中间产物为主, 并保持以热变速率为(0.9799±0.5356) μJ/s稳定放热, 为拟零级反应过程, 是光催化反应的决速步骤.  相似文献   

8.
通过水热和原位还原法制备了一种新型Z型异质结三元复合材料Au NPs/g-C3N4/BiOBr,并通过X射线衍射、X射线光电子能谱、透射电子显微镜、紫外-可见漫反射光谱和光致发光发射光谱等技术对材料的形貌、结构进行了表征。通过在可见光下降解苯酚来评价光催化剂的活性。研究发现,Au NPs/g-C3N4/BiOBr显示出增强的光催化活性,对苯酚的降解能力是g-C3N4的3倍,是BiOBr的2.5倍。这可归因于三元复合材料的窄带隙(2.10eV)、Z型机理对光生电子-空穴对的有效分离和Au纳米颗粒的表面等离子体共振效应(SPR)。  相似文献   

9.
分别采用热解法和溶胶-凝胶-碳热还原法合成了石墨相氮化碳(g-C3N4)和纳米级碳化硅(β-SiC), 通过浸渍-热处理法将两者复合并通过浓盐酸质子化, 分别制备了g-C3N4/β-SiC和质子化g-C3N4/β-SiC(P-g-C3N4/β-SiC)复合光催化剂. 利用X射线衍射(XRD)、 扫描电子显微镜(SEM)、 高分辨透射电子显微镜(HRTEM)、 傅里叶变换红外光谱(FTIR)、 X射线光电子能谱(XPS)、 紫外-可见漫反射光谱(UV-Vis-DRS)和光致发光光谱(PL)等对样品进行了表征. 结果表明, P-g-C3N4/β-SiC复合材料的比表面积增大, 光生电子-空穴对的复合几率降低, 光催化性能明显提高. 在光催化降解染料茜素红(ARS)研究中, 样品的可见光催化活性顺序为P-g-C3N4/β-SiC>g-C3N4/β-SiC>P-g-C3N4>g-C3N4>β-SiC. 其中P-g-C3N4/β-SiC在60 min内对ARS的降解效率高达99.9%, 符合准一阶动力学模型, 速率常数为0.0967 min -1, 且循环使用9次后, 光催化降解效率仍保持97.5%以上.  相似文献   

10.
通过将BiOBr纳米片与g-C3N4复合,然后原位还原,合成了具有纳米花状结构的三元异质结光催化剂g-C3N4/Bi/BiOBr.对g-C3N4/Bi/BiOBr的结构、形貌、元素价态和光学性能等进行了表征和研究.评估了g-C3N4/Bi/BiOBr对气体甲醛的光催化降解活性. g-C3N4/Bi/BiOBr在可见光照射下降解甲醛的活性与g-C3N4、 BiOBr单体和g-C3N4/BiOBr二元复合物相比显著提高. 20%-g-C3N4/Bi/BiOBr复合物可以在60 min内(λ> 400 nm)降解80%的气态甲醛(初始浓度0.16 mg·L-1).  相似文献   

11.
刘优昌  王亮 《燃料化学学报》2018,46(9):1146-1152
以三聚氰胺作为合成g-C_3N_4纳米片的前躯体,以Bi(NO3)3·5H2O和KBr作为合成BiOBr的原料,采用水热法构建g-C_3N_4/Bi OBr二维异质结可见光催化剂,有效的晶面复合和合适的能带组合有助于增强g-C_3N_4和BiOBr的可见光催化活性。利用X射线衍射(XRD)、透射电镜(TEM)、X射线光电子能谱(XPS)、光致发光光谱(PL)和紫外-可见漫反射光谱(UVvis DRS)等方法表征其结构、光学性质以及组成结构。在可见光(λ420 nm)下以光催化降解RhB来评价合成催化剂的光催化活性,结果表明,g-C_3N_4/BiOBr光催化降解罗丹明B(Rh B)的效率高于单体g-C_3N_4和BiOBr,并对g-C_3N_4/BiOBr增强可见光催化RhB机理进行解释。  相似文献   

12.
Photocatalytic reduction of CO2 to hydrocarbon compounds is a promising method for addressing energy shortages and environmental pollution. Considerable efforts have been devoted to exploring valid strategies to enhance photocatalytic efficiency. Among various modification methods, the hybridization of different photocatalysts is effective for addressing the shortcomings of a single photocatalyst and enhancing its CO2 reduction performance. In addition, metal-free materials such as g-C3N4 and black phosphorus (BP) are attractive because of their unique structures and electronic properties. Many experimental results have verified the superior photocatalytic activity of a BP/g-C3N4 composite. However, theoretical understanding of the intrinsic mechanism of the activity enhancement is still lacking. Herein, the geometric structures, optical absorption, electronic properties, and CO2 reduction reaction processes of 2D/2D BP/g-C3N4 composite models are investigated using density functional theory calculations. The composite model consists of a monolayer of BP and a tri-s-triazine-based monolayer of g-C3N4. Based on the calculated work function, it is inferred that electrons transfer from g-C3N4 to BP owing to the higher Fermi level of g-C3N4 compared with that of BP. Furthermore, the charge density difference suggests the formation of a built-in electric field at the interface, which is conducive to the separation of photogenerated electron-hole pairs. The optical absorption coefficient demonstrates that the light absorption of the composite is significantly higher than that of its single-component counterpart. Integrated analysis of the band edge potential and interfacial electronic interaction indicates that the migration of photogenerated charge carriers in the BP/g-C3N4 hybrid follows the S-scheme photocatalytic mechanism. Under visible-light irradiation, the photogenerated electrons on BP recombine with the photogenerated holes on g-C3N4, leaving photogenerated electrons and holes in the conduction band of g-C3N4 and the valence band of BP, respectively. Compared with pristine g-C3N4, this S-scheme heterojunction allows efficient separation of photogenerated charge carriers while effectively preserving strong redox abilities. Additionally, the possible reaction path for CO2 reduction on g-C3N4 and BP/g-C3N4 is discussed by computing the free energy of each step. It was found that CO2 reduction on the composite occurs most readily on the g-C3N4 side. The reaction path on the composite is different from that on g-C3N4. The heterojunction reduces the maximum energy barrier for CO2 reduction from 1.48 to 1.22 eV, following the optimal reaction path. Consequently, the BP/g-C3N4 heterojunction is theoretically proven to be an excellent CO2 reduction photocatalyst. This work is helpful for understanding the effect of BP modification on the photocatalytic activity of g-C3N4. It also provides a theoretical basis for the design of other high-performance CO2 reduction photocatalysts.   相似文献   

13.
Limited visible-light absorption and high recombination rate of photogenerated charges are two main drawbacks in g-C3N4-based photocatalysts. To solve these problems, g-C3N4/nitrogen-doped graphene quantum dots (NGQDs)/TiO2 ternary heterojunctions were facilely prepared via a one-step calcining method. The morphology, structure, optical and electrochemical properties of g-C3N4/NGQDs/TiO2 were characterized and explored. The optimal g-C3N4/NGQDs/TiO2 composite exhibits enhanced photocatalytic degradation performance of ciprofloxacin (CIP) compared with the as-prepared g-C3N4, TiO2(P25) and g-C3N4/TiO2 heterojunction under visible light irradiation. The apparent rate constant of the composite is around 6.43, 4.03 and 2.30 times higher than those of g-C3N4, TiO2 and g-C3N4/TiO2, respectively. The enhanced photocatalytic efficiency should be mainly attributed to the improvement of light absorption and charge separation and transfer efficiency, originating from the narrow band gap and high charge carrier mobility. The active species trapping experiments results showed that the h+ and ·O2- were the main active species in the degradation process. A possible photocatalytic reaction mechanism of the g-C3N4/NGQDs/TiO2 composite for the enhanced degradation of CIP under visible light irradiation was also proposed.  相似文献   

14.
Organic photocatalysts have attracted attention owing to their suitable redox band positions, low cost, high chemical stability, and good tunability of their framework and electronic structure. As a novel organic photocatalyst, PDI-Ala (N, N'-bis(propionic acid)-perylene-3, 4, 9, 10-tetracarboxylic diimide) has strong visible-light response, low valence band position, and strong oxidation ability. However, the low photogenerated charge transfer rate and high carrier recombination rate limit its application. Due to the aromatic heterocyclic structure of g-C3N4 and large delocalized π bond in the planar structure of PDI-Ala, g-C3N4 and PDI-Ala can be tightly combined through π–π interactions and N―C bond. The band structure of sulfur-doped g-C3N4 (S-C3N4) matched well with PDI-Ala than that with g-C3N4. The electron delocalization effect, internal electric field, and newly formed chemical bond jointly promote the separation and migration of photogenerated carriers between PDI-Ala and S-C3N4. To this end, a novel step-scheme (S-scheme) heterojunction photocatalyst comprising organic semiconductor PDI-Ala and S-C3N4 was prepared by an in situ self-assembly strategy. Meanwhile, PDI-Ala was self-assembled by transverse hydrogen bonding and longitudinal π–π stacking. The crystal structure, morphology, valency, optical properties, stability, and energy band structure of the PDI-Ala/S-C3N4 photocatalysts were systematically analyzed and studied by various characterization methods such as X-ray diffraction, transmission electron microscopy, energy dispersive X-ray spectrometry, X-ray photoelectron spectroscopy, ultraviolet visible diffuse reflectance spectroscopy, electrochemical impedance spectroscopy, and Mott-Schottky curve. The work functions and interface coupling characteristics were determined using density functional theory. The photocatalytic activities of the synthesized photocatalyst for H2O2 production and the degradation of tetracycline (TC) and p-nitrophenol (PNP) under visible-light irradiation are discussed. The PDI-Ala/S-C3N4 S-scheme heterojunction with band matching and tight interface bonding accelerates the intermolecular electron transfer and broadens the visible-light response range of the heterojunction. In addition, in the processes of the PDI-Ala/S-C3N4 photocatalytic degradation reaction, a variety of active species (h+, ·O2-, and H2O2) were produced and accumulated. Therefore, the PDI-Ala/S-C3N4 heterojunction exhibited enhanced photocatalytic performance in the degradation of TC, PNP, and H2O2 production. Under visible-light irradiation, the optimum 30%PDI-Ala/S-C3N4 removed 90% of TC within 90 min. In addition, 30%PDI-Ala/S-C3N4 displayed the highest H2O2 evolution rate of 28.3 μmol·h-1·g-1, which was 2.9 and 1.6 times higher than those of PDI-Ala and S-C3N4, respectively. These results reveal that the all organic photocatalyst comprising PDI-based supramolecular and S-C3N4 can be efficiently applied for the degradation of organic pollutants and production of H2O2. This work not only provides a novel strategy for the design of all organic S-scheme heterojunctions but also provides a new insight and reference for understanding the structure–activity relationship of heterostructure catalysts with effective interface bonding.   相似文献   

15.
通过硬模板法,采用氰胺前驱物和二氧化硅纳米管(SiO2-NTs)模板,合成石墨相氮化碳纳米管(CN-NTs)光催化剂。采用扫描电镜(SEM)、透射电镜(TEM)、X射线粉末衍射(XRD)、傅立叶变换红外光谱(FT-IR)、氮气吸附/脱附测试、紫外可见漫反射光谱(UV-Vis DRS)、荧光光谱、热重分析(TGA)等手段对CN-NTs催化剂的结构与性能进行表征。结果表明,CN-NTs的化学组成是石墨相氮化碳(g-C3N4),形貌为均匀的纳米管,且是介孔材料。与体相氮化碳(B-CN)和介孔石墨相氮化碳(mpg-CN)相比,CN-NTs的光吸收带边蓝移到440 nm,荧光发射谱的峰强减弱。在可见光(λ>420 nm)照射下,CN-NTs具有较高的光催化分解水活性,产氢速率为58 μmol/h,且表现出良好的光催化活性稳定性和化学结构稳定性。研究结果表明纳米管状结构能有效促进g-C3N4半导体激子解离,提高光生电子-空穴的分离效率,进而显著优化g-C3N4的光催化产氢性能。  相似文献   

16.
研究了用离子交换沉淀法制备的Ag/Ag3PO4/g-C3N4的可见光光催化性能及再生方法.通过X射线衍射(XRD)、场发射扫描电子显微镜(FESEM)、紫外-可见(UV-Vis)吸收光谱及X射线光电子能谱(XPS)对其进行了结构特性分析.XRD结果显示再生后催化剂的结构未发生改变.FESEM及UV-Vis分析结果说明催化剂由Ag3PO4与g-C3N4复合而成.XPS分析结果表明催化剂表面出现少量的银单质.利用可见光(λ420nm)照射下的苯酚降解实验评价了样品的光催化活性,并通过活性物种及能带结构的分析对催化剂的光催化机理进行了推测.研究表明,Ag/Ag3PO4/g-C3N4的光催化活性明显高于纯Ag3PO4及纯g-C3N4,主要原因归结为单质银、Ag3PO4及g-C3N4的协同效应.经过氧化氢和磷酸氢铵钠(NaNH4HPO4)的再生可完全恢复催化剂的活性,这表明该绿色环保的再生方法可实现Ag/Ag3PO4/g-C3N4催化剂在环境中的实际应用.  相似文献   

17.
Photocatalytic technology can effectively solve the problem of increasingly serious water pollution, the core of which is the design and synthesis of highly efficient photocatalytic materials. Semiconductor photocatalysts are currently the most widely used photocatalysts. Among these is graphitic carbon nitride (g-C3N4), which has great potential in environment management and the development of new energy owing to its low cost, easy availability, unique band structure, and good thermal stability. However, the photocatalytic activity of g-C3N4 remains low because of problems such as wide bandgap, weakly absorb visible light, and the high recombination rate of photogenerated carriers. Among various modification strategies, doping modification is an effective and simple method used to improve the photocatalytic performance of materials. In this work, Cu/g-C3N4 photocatalysts were successfully prepared by incorporating Cu2+ into g-C3N4 to further optimize photocatalytic performance. At the same time, the structure, morphology, and optical and photoelectric properties of Cu/g-C3N4 photocatalysts were analyzed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy, UV-Vis diffuse reflectance spectroscopy (DRS), and photoelectric tests. XRD and XPS were used to ensure that the prepared photocatalysts were Cu/g-C3N4 and the valence state of Cu was in the form of Cu2+. Under visible light irradiation, the photocatalytic activity of Cu/g-C3N4 and pure g-C3N4 photocatalysts were investigated in terms of the degradation of RhB and CIP by comparing the amount of introduced copper ions. The experimental results showed that the degradation ability of Cu/g-C3N4 photocatalysts was stronger than that of pure g-C3N4. The N2 adsorption-desorption isotherms of g-C3N4 and Cu/g-C3N4 demonstrated that the introduction of copper had little effect on the microstructure of g-C3N4. The small difference in specific surface area indicates that the enhanced photocatalytic activity may be attributed to the effective separation of photogenerated carriers. Therefore, the enhanced photocatalytic degradation of RhB and CIP over Cu/g-C3N4 may be due to the reduction of carrier recombination rate by copper. The photoelectric test showed that the incorporation of Cu2+ into g-C3N4 could reduce the electron-hole recombination rate of g-C3N4 and accelerate the separation of electron-hole pairs, thus enhancing the photocatalytic activity of Cu/g-C3N4. Free radical trapping experiments and electron spin resonance indicated that the synergistic effect of superoxide radicals (O2•−), hydroxyl radicals (•OH) and holes could increase the photocatalytic activity of Cu/g-C3N4 materials.  相似文献   

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