g-C3N4基复合分离膜的制备及光催化性能

利用g-C₃N₄纳米片表面的氨基与膜基底材料氯甲基化聚醚砜（CMPES）的苄氯基团发生化学交联反应,再通过相转化法制备出g-C₃N₄/CMPES复合膜。系统研究了g-C₃N₄纳米片的添加对复合膜的结构、形貌及过滤、光催化、抗污染性能的影响,并探讨其光催化降解牛血清白蛋白溶液（BSA）的机理。研究结果表明：g-C₃N₄纳米片与膜基底材料通过化学键相连接,有效提高了复合膜的光催化性能和稳定性。由于g-C₃N₄纳米片的亲水性和光催化作用,使复合膜表现出优异的过滤性能和抗污染性能。     

One-Step Calcination to Gain Exfoliated g-C3N4/MoO2 Composites for High-Performance Photocatalytic Hydrogen Evolution

The difficulty of exposing active sites and easy recombination of photogenerated carriers have always been two critical problems restricting the photocatalytic activity of g-C₃N₄. Herein, a simple (NH₄)₂MoO₄-induced one-step calcination method was successfully introduced to transform bulk g-C₃N₄ into g-C₃N₄/MoO₂ composites with a large specific surface area. During the calcination, with the assistance of NH₃ and water vapor produced by ammonium molybdate, the pyrolytical oxidation and depolymerization of a g-C₃N₄ interlayer were accelerated, finally realizing the exfoliation of the g-C₃N₄. Furthermore, another pyrolytical product of ammonium molybdate was transformed into MoO₂ under an NH₃ atmosphere, which was in situ loaded on the surface of a g-C₃N₄ nanosheet. Additionally, the results of photocatalytic hydrogen evolution under visible light show that the optimal g-C₃N₄/MoO₂ composite has a high specific surface area and much improved performance, which is 4.1 times that of pure bulk g-C₃N₄. Such performance improvement can be attributed to the full exposure of active sites and the formation of abundant heterojunctions. However, with an increasing feed amount of ammonium molybdate, the oxidation degree of g-C₃N₄ was enhanced, which would widen the band gap of g-C₃N₄, leading to a weaker response ability to visible light. The present strategy will provide a new idea for the simple realization of exfoliation and constructing a heterojunction for g-C₃N₄ simultaneously.     

Ag/Ag3PO4/g-C3N4三元复合光催化剂的制备及其可见光驱动下的光催化活性增强

报道了一种新型Ag/Ag₃PO₄/g-C₃N₄三元复合光催化剂的制备及其半导体界面处的快速载流子分离所引起的光催化活性的显著增强效应。通过X射线衍射,扫描电子显微镜,紫外-可见吸收光谱以及光致发光光谱等就其晶体结构、形貌、组分、光学吸收以及载流子的快速分离行为进行了表征与分析。以罗丹明B作为模型化合物分子,研究发现,所制备的Ag/Ag₃PO₄/g-C₃N₄三元复合光催化剂在可见光照射下表现出比Ag₃PO₄以及Ag₃PO₄/g-C₃N₄二元催化剂更为优异的光催化活性。研究认为,Ag₃PO₄表面尺寸约为40 nm的Ag纳米粒子在可见光下受激所产生的等离子表面共振效应以及Ag₃PO₄与g-C₃N₄界面处所形成的类似异质结结构对所制备的Ag/Ag₃PO₄/g-C₃N₄三元复合光催化剂光催化活性的显著增强起到重要作用。     

分级孔结构g-C3N4光催化剂的制备及性能

以单分散SiO2为模板,通过简单的一步煅烧法制备具有分级孔结构的g-C3N4。与体相g-C3N4相比,分级孔结构的g-C3N4不仅可见光吸收性能和比表面积得到提高,而且更有利于光生电子-空穴的分离。此外,具有分级孔结构的g-C3N4具有明显增强的可见光驱动的光催化产氢活性,当SiO2和二氰二胺质量比为1∶1时,制备所得g-C3N4(C3N4-2)产氢速率几乎是体相g-C3N4的18倍。     

Highly Efficient Ag3PO4/g-C3N4 Z-Scheme Photocatalyst for Its Enhanced Photocatalytic Performance in Degradation of Rhodamine B and Phenol

Ag₃PO₄/g-C₃N₄ heterojunctions, with different g-C₃N₄ dosages, were synthesized using an in situ deposition method, and the photocatalytic performance of g-C₃N₄/Ag₃PO₄ heterojunctions was studied under simulated sunlight conditions. The results revealed that Ag₃PO₄/g-C₃N₄ exhibited excellent photocatalytic degradation activity for rhodamine B (Rh B) and phenol under the same light conditions. When the dosage of g-C₃N₄ was 30%, the degradation rate of Rh B at 9 min and phenol at 30 min was found to be 99.4% and 97.3%, respectively. After five cycles of the degradation experiment for Rh B, g-C₃N₄/Ag₃PO₄ still demonstrated stable photodegradation characteristics. The significant improvement in the photocatalytic activity and stability of g-C₃N₄/Ag₃PO₄ was attributed to the rapid charge separation between g-C₃N₄ and Ag₃PO₄ during the Z-scheme charge transfer and recombination process.     

Photocatalytic Aerobic Oxidation of Biomass-Derived 5-HMF to DFF over MIL-53(Fe)/g-C3N4 Composite

A MIL-53(Fe)/g-C₃N₄ heterogeneous composite was synthesized and applied in photocatalytic oxidation of 5-hydroxymethylfurfural (5-HMF) to 2,5-diformylfuran (DFF). The systematic investigation indicated that the introduction of MIL-53(Fe) into g-C₃N₄ increased the specific surface area, broadened the visible-light response region, and promoted the separation efficiency of the photo-generated electron-hole pairs. The 10% MIL-53(Fe)/g-C₃N₄ heterogeneous composite achieved the best photocatalytic oxidation activity with 74.5% of 5-HMF conversion under simulated sunlight, which was much higher than that of pristine g-C₃N₄ and MIL-53(Fe). The MIL-53(Fe)/g-C₃N₄ composite displayed good photocatalytic reusability and stability. Based on the characterization results and photocatalytic performance, a Z-scheme photocatalytic mechanism of the MIL-53(Fe)/g-C₃N₄ composite was suggested, and a possible reaction route was deduced.     

MoS_2/g-C_3N_4复合材料的制备及可见光催化性能

首先在N-甲基吡咯烷酮溶液中超声剥离得到少层的MoS_2,将其与石墨相氮化碳(g-C_3N_4)复合,制得MoS_2/g-C_3N_4复合材料。采用X射线衍射(XRD),扫描电镜(SEM),X射线光电子能谱(XPS),傅里叶变换红外光谱(FTIR),Raman光谱,紫外-可见漫反射吸收光谱(DRS)和光致荧光(PL)技术对复合材料进行表征。可见光下考察MoS_2/g-C_3N_4复合材料光催化降解罗丹明B(Rh B)的活性,结果表明:将少量MoS_2与g-C_3N_4复合可明显提高光催化活性,且1%(w/w)MoS_2/g-C_3N_4复合物的光催化活性最高,可能的原因是MoS_2和g-C_3N_4匹配的能带结构,增大了界面间电荷的传输,降低了光生电子-空穴的复合,进而提高了光催化活性。     

g-C3N4纳米管的制备及其光催化降解性能

以三聚氰胺和碳酸氢铵混合物为原料,采用简便热解法制备g-C₃N₄纳米管。热解过程中碳酸氢铵分解释放出大量的NH₃,能够诱导纳米管的形成。利用X射线衍射（XRD）、扫描电子显微镜（SEM）、红外光谱（IR）、N₂吸附-脱附、紫外-可见漫反射光谱以及紫外可见光谱（UV）等分析测试方法对该光催化剂的微观形貌结构和催化性能进行了表征。以罗丹明光催化降解为模型反应研究了g-C₃N₄纳米管的光催化活性。g-C₃N₄纳米管的表面积明显增大,且能够有效地促进光生电子转移,在可见光下具有较强的光催化性能,降解率在60和120 min时分别能达到95%和99.4%,且循环重复利用5次后降解率不低于92%。     

MoS2/g-C3N4复合材料的制备及可见光催化性能

首先在N-甲基吡咯烷酮溶液中超声剥离得到少层的MoS₂,将其与石墨相氮化碳（g-C₃N₄）复合,制得MoS₂/g-C₃N₄复合材料。采用X射线衍射（XRD）,扫描电镜（SEM）,X射线光电子能谱（XPS）,傅里叶变换红外光谱（FTIR）,Raman光谱,紫外-可见漫反射吸收光谱（DRS）和光致荧光（PL）技术对复合材料进行表征。可见光下考察MoS₂/g-C₃N₄复合材料光催化降解罗丹明B（RhB）的活性,结果表明：将少量MoS₂与g-C₃N₄复合可明显提高光催化活性,且1%（w/w）MoS₂/g-C₃N₄复合物的光催化活性最高,可能的原因是MoS₂和g-C₃N₄匹配的能带结构,增大了界面间电荷的传输,降低了光生电子-空穴的复合,进而提高了光催化活性。     

石墨相氮化碳/二氧化锡复合材料的制备及光催化性能

采用热聚合法和水热法相结合的方法制备了g-C_3N_4/SnO_2复合光催化剂。利用XRD、SEM、TEM、FT-IR和UV-Vis DRS等多种测试手段对所得样品的物相结构、微观形貌和吸光特性等进行了表征。结果表明,异质结构复合光催化剂的最大光吸收边位置相对纯相SnO_2发生了明显的红移,并且SnO_2颗粒均匀分布于g-C_3N_4表面,其中最优组分(50%-g-C_3N_4/SnO_2)光催化降解染料罗丹明B(RhB)的效率达到了纯相g-C_3N_4的3.78倍。     

凹凸棒石/g-C3N4-AgFeO2复合材料制备及其光催化性能

以凹凸棒石(简称凹土,ATP)为基体,通过原位化学法一步直接合成g-C_3N_4薄层材料,并将其有效固载于凹土表面(ATP/gC_3N_4),再通过原位沉淀法引入不同比例AgFeO_2纳米颗粒,构筑系列兼具磁分离特性和高效光催化活性的ATP/g-C_3N_4-AgFeO_2-Y复合光催化剂(Y=wATP/g-C_3N_4/(wATP/g-C_3N_4+wAg FeO_2)×100%,表示ATP/g-C_3N_4在ATP/g-C_3N_4-AgFeO_2复合材料中所占的质量百分数)。采用XRD、SEM、BET、UV-Vis、PL和ICP表征其结构和物化性能,以酸性红G(ARG)为目标降解物,研究其光催化性能。研究发现:通过形成Si-O-C键,g-C_3N_4薄层被均匀固定在凹土表面;AgFeO_2纳米颗粒均匀沉积于ATP/g-C_3N_4表面并形成Z型异质结,ATP/gC_3N_4-AgFeO_2-Y具有比ATP/g-C_3N_4和AgFeO_2更优异的可见光光催化性能,且随着ATP/g-C_3N_4含量的增大呈先升高而后下降的趋势;当Y=57%时复合材料的性能最佳,ATP/g-C_3N_4-AgFeO_2-57%对20 mg·L-1酸性红G的降解率可达97.4%,循环4次使用后,降解率仍保持94.2%。通过自由基捕获实验研究了光催化反应机理,发现·O2-是光催化过程的主要活性物种。     

g-C3N4纳米管的制备及其光催化降解性能

以三聚氰胺和碳酸氢铵混合物为原料,采用简便热解法制备g-C_3N_4纳米管。热解过程中碳酸氢铵分解释放出大量的NH3,能够诱导纳米管的形成。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、红外光谱(IR)、N_2吸附-脱附、紫外-可见漫反射光谱以及紫外可见光谱(UV)等分析测试方法对该光催化剂的微观形貌结构和催化性能进行了表征。以罗丹明光催化降解为模型反应研究了g-C_3N_4纳米管的光催化活性。g-C_3N_4纳米管的表面积明显增大,且能够有效地促进光生电子转移,在可见光下具有较强的光催化性能,降解率在60和120 min时分别能达到95%和99.4%,且循环重复利用5次后降解率不低于92%。     

Synergistic improvement of Cr(VI) reduction and RhB degradation using RP/g-C3N4 photocatalyst under visible light irradiation

The RP/g-C₃N₄ heterojunction photocatalyst was fabricated by a facile heat treatment strategy. The obtained composite has excellent light harvesting ability and charge separation performance. Compared to single RP and g-C₃N₄, the 50%-RP/g-C₃N₄ exhibited enhanced photocatalytic activity for simultaneously removing Cr(VI) and RhB, and the removal rates can reach 92% and 99% in 25 min, respectively. The enhanced mechanism was revealed by active species capturing experiments, showing that electrons can reduce Cr(VI) and produce O₂^– in air and that holes can directly oxidize the dyes. The coexistence of Cr(VI) and RhB will lead to a synergistic improvement of Cr(VI) reduction and RhB degradation due to rapid surface reactions. This further improves the charge separation except for the heterojunction effect. In addition, the COD analysis demonstrates that organic dyes are mainly degraded into CO₂, H₂O and some intermediates.     

g-C3N4-BiOBr复合材料制备及可见光催化性能

利用原位沉积法将BiOBr纳米片生长到g-C₃N₄表面,制得g-C₃N₄-BiOBr p-n型异质结复合光催化剂。采用X射线衍射(XRD)、红外光谱(FTIR)、场发射扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)、紫外可见漫反射(UV-Vis-DRS)和荧光光谱(PL)等测试对光催化剂结构和性能进行表征。通过可见光辐照降解甲基橙水溶液检测评估复合光催化剂光催化活性。研究结果表明:复合光催化剂由BiOBr和g-C₃N₄两相组成,BiOBr纳米片在片状g-C₃N₄表面快速形核生长形成面-面复合结构。相比于纯相g-C₃N₄和BiOBr,g-C₃N₄-BiOBr复合材料具有更强可见光吸收能力,吸收带边红移。在可见光辐照100 min后,性能最佳的2:8 g-C₃N₄-BiOBr复合光催化剂光催化活性分别是纯相g-C₃N₄和BiOBr的1.8和1.2倍,经过4次循环实验后,其降解率仍达84%,说明复合结构光催化剂催化性能和稳定性增强。复合光催化剂的荧光强度显著降低,说明光生载流子复合得到了有效抑制。复合光催化剂催化性能的提高归因于p-n型异质结促进电荷有效分离、抑制电子-空穴复合和吸收光波长范围的扩展,相比单一成分材料具有更好的催化活性和稳定性。自由基捕获实验证明,可见光降解甲基橙光催化过程中的主要活性成分为空穴,并据此提出了可能的光催化机理。     

一锅法制备Co3O4/g-C3N4复合光催化剂及其光催化性能

以三聚氰胺和六水合氯化钴为原料,一锅法制备Co_3O_4负载的多孔石墨相氮化碳(Co_3O_4/g-C_3N_4)复合光催化材料。采用X射线衍射(XRD)、傅里叶变换红外(FT-IR)光谱、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-可见漫反射光谱(UV-Vis DRS)、光致发光光谱(PL)等手段对其结构和光学特性进行表征。以盐酸四环素(TC)为目标污染物,评价了不同负载量Co_3O_4/g-C_3N_4复合光催化剂的可见光催化性能。结果表明,所制备的Co_3O_4/g-C_3N_4复合光催化剂为多孔结构,其比表面积较大,并在可见光区域具有显著的吸收。利用原位生成的Co_3O_4纳米粒子在氮化碳表面形成异质结构,可有效转移光生载流子,降低光生电子-空穴的再结合率,从而提高光催化活性。并且存在最佳Co_3O_4复合量,当六水合氯化钴加入量为三聚氰胺的8%(w/w)时,所制备的复合光催化剂CoCN-8具有最佳的光催化性能。在可见光的照射下,60 min内可降解85%的TC,而同样条件下,纯g-C_3N_4仅降解23%的TC。     

g-C3N4-BiOBr复合材料制备及可见光催化性能

利用原位沉积法将Bi OBr纳米片生长到g-C_3N_4表面,制得g-C_3N_4-Bi OBr p-n型异质结复合光催化剂。采用X射线衍射(XRD)、红外光谱(FTIR)、场发射扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)、紫外可见漫反射(UV-Vis-DRS)和荧光光谱(PL)等测试对光催化剂结构和性能进行表征。通过可见光辐照降解甲基橙水溶液检测评估复合光催化剂光催化活性。研究结果表明:复合光催化剂由Bi OBr和g-C_3N_4两相组成,Bi OBr纳米片在片状g-C_3N_4表面快速形核生长形成面-面复合结构。相比于纯相g-C_3N_4和Bi OBr,g-C_3N_4-Bi OBr复合材料具有更强可见光吸收能力,吸收带边红移。在可见光辐照100 min后,性能最佳的2:8 gC_3N_4-Bi OBr复合光催化剂光催化活性分别是纯相g-C_3N_4和Bi OBr的1.8和1.2倍,经过4次循环实验后,其降解率仍达84%,说明复合结构光催化剂催化性能和稳定性增强。复合光催化剂的荧光强度显著降低,说明光生载流子复合得到了有效抑制。复合光催化剂催化性能的提高归因于p-n型异质结促进电荷有效分离、抑制电子-空穴复合和吸收光波长范围的扩展,相比单一成分材料具有更好的催化活性和稳定性。自由基捕获实验证明,可见光降解甲基橙光催化过程中的主要活性成分为空穴,并据此提出了可能的光催化机理。     

单分散g-C3N4量子点修饰一维棒状BiPO4微晶的合成及其对光催化活性增强机理

利用水热法合成了一维棒状BiPO₄微晶,在此基础上采用浸渍-被烧法进行g-C₃N₄量子点表面修饰获得新颖的g-C₃N₄/BiPO₄异质结。借助X射线衍射(XRD)、场发射扫描电镜(FE-SEM)、透射电镜(HRTEM)、能谱(EDS)、紫外-可见漫反射(UV-Vis-DRS)等测试手段对所得样品的相组成、形貌和谱学特征进行了表征。选择罗丹明B(RhB)和苯酚作为模型污染物研究了所得在可见光下的催化活性。结果表明,样品16%(w/w) g-C₃N₄/BiPO₄对RhB降解的速率常数分别是纯和的g-C₃N₄和BiPO₄的16倍和4.6倍。g-C₃N₄量子点与BiPO₄之间形成异质结,抑制了光生电子-空穴对的复合,从而提高了催化剂的活性。自由基捕获实验进一步表明,超氧负离子自由基(·O₂-)是催化降解RhB和苯酚的主要活性物种。     

中空管状g-C3N4/Ag3PO4复合催化剂的制备及其可见光催化性能

用化学沉淀法制备中空管状g-C₃N₄/Ag₃PO₄复合催化剂。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外可见漫反射光谱(UV-Vis DRS)和荧光光谱对其结构、形貌和光学性能进行了表征。结果表明：Ag₃PO₄纳米颗粒均匀地分散在中空管状g-C₃N₄表面,两者紧密结合形成异质结。研究复合催化剂在可见光照射下降解盐酸四环素(TC)的光催化活性。结果显示：复合催化剂在80 min内对TC的降解率为98%,其降解反应速率常数是纯相Ag₃PO₄的3倍。经过5次循环实验后复合催化剂对于TC的降解率仍保持87%,具有优良的循环稳定性。捕获实验表明空穴(h⁺)和超氧负离子(·O^-₂)是光催化反应过程中的主要活性物种。根据能带理论,提出了复合催化剂异质结的Z型光催化机理。     

Synthesis of Porous Carbon Nitride Nanobelts for Efficient Photocatalytic Reduction of CO2

Sustainable conversion of CO₂ to fuels using solar energy is highly attractive for fuel production. This work focuses on the synthesis of porous graphitic carbon nitride nanobelt catalyst (PN-g-C₃N₄) and its capability of photocatalytic CO₂ reduction. The surface area increased from 6.5 m²·g⁻¹ (graphitic carbon nitride, g-C₃N₄) to 32.94 m²·g⁻¹ (PN-g-C₃N₄). C≡N groups and vacant N_2C were introduced on the surface. PN-g-C₃N₄ possessed higher absorbability of visible light and excellent photocatalytic activity, which was 5.7 and 6.3 times of g-C₃N₄ under visible light and simulated sunlight illumination, respectively. The enhanced photocatalytic activity may be owing to the porous nanobelt structure, enhanced absorbability of visible light, and surface vacant N-sites. It is expected that PN-g-C₃N₄ would be a promising candidate for CO₂ photocatalytic conversion.     

Synthesis g-C3N4 of high specific surface area by precursor pretreatment strategy with SBA-15 as a template and their photocatalytic activity toward degradation of rhodamine B

Using SBA-15 as a template, high surface area porous graphitic carbon nitrides (g-C₃N₄) were successfully synthesized by pretreating melamine using hydrochloric acid, and fully characterized by Fourier-Transform infrared (FT-IR), X-ray diffraction (XRD), scanning electron micrographs (SEM), N₂ adsorption-desorption, ultraviolet-visible (UV-Vis) spectroscopy, photoluminescence (PL) spectrum. The results of these analyses indicated that the g-C₃N₄ synthesized from HCl-pretreated melamine with SBA-15 as a template has enhanced specific surface area and increased the separation rate of the photogenerated electrons and holes compared with bulk g-C₃N₄, but didn’t change the structure of bulk g-C₃N₄. The photocatalytic activity of samples was evaluated by the degradation of rhodamine B (RhB) under xenon lamp. The results indicated that the activity was improved significantly with the increase of specific surface area. The rate constant for CN-3（HCl pretreatment melamine precursor and SBA-15 as a template） was 13 times as high as g-C₃N₄. Furthermore, the CN-3 catalyst exhibited outstanding structural and catalytic stability.