石墨烯/二氧化钛杂化材料的制备及其催化的光解水制氢
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摘要
日益增长的能源需求、化石能源的逐渐枯竭以及使用核能带来的环境问题,促进了对洁净可再生替代能源的研究热潮。环境友好的氢能是潜在的替代能源之一,有益于同时解决能源和环境问题。然而,与之相关的氢能生产、储存、运输和使用问题均存在不小的挑战。就氢气的制备而言,当前仍是基于化石燃料的转换,满足不了低碳经济的要求,同时还以消耗化石能源为代价；而利用太阳能以半导体为光催化剂光催化分解水制氢则被认为是最终解决能源问题的有效途径之一。
为了实现有效地光催化分解水制氢,研究者对半导体光催化剂进行了广泛的探索。二氧化钛被认为是一种重要的光催化剂,具有优异的光电性能、化学稳定性、低成本等优点。催化剂的光吸收能力、能级水平及光生载流子的转换过程,包括光生载流子的产生、复合、分离、迁移和捕获等,都影响光催化制氢的效率。3.2eV的宽带隙导致二氧化钛对太阳光的利用率低,在很大程度上限制了二氧化钛在光催化方面的应用。为了拓展二氧化钛的光吸收范围,形态修饰、非金属元素(C、N、S、P等)的掺杂等是普遍采用的措施。
另一方面,石墨烯是一种性能优异的碳材料,在室温下具有较高的载流子迁移率(>200000cm2V-1s-1)。基于石墨烯的半导体杂化材料研究取得了很大的进展,其中包括二氧化钛与石墨烯的杂化材料。已有报道表明石墨烯可阻止载流子的复合、促进电荷的转移并提高光催化分解水制氢的效率。
为获得可见光驱动的、稳定和高效的光催化剂用于太阳能光催化分解水制氢,本论文从二氧化钛的氮掺杂、石墨烯的改性、引入染料作为光敏剂三个方面着手,或者这几个方面的综合应用,制备了一系列二氧化钛与石墨烯的杂化材料。分别利用红外光谱(FTIR)、X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、拉曼光谱、原子力显微镜(AFM)、X射线光电子能(XPS)等手段对所制备材料进行了表征。以甲醇水溶液作为光催化产氢体系,通过在线气相色谱仪检测评价了这些材料的光催化活性。
首先,利用Hummers方法从石墨制备石墨氧化物(GO)。GO含有羟基、羧基等含氧官能团,具有很高的水溶性。通过硼氢化钠还原,GO中的共轭结构得到了重建,该产物称之为酸化石墨烯(RG-COOH)=P25与RG-COOH混合得到二氧化钛与酸化石墨烯的杂化材料TRG-COOH.结果证明,由于RG-COOH的引入,杂化材料的带隙从P25的3.25eV降低到2.80eV。TRG-COOH的光催化制氢效率从P25的8.2μmol h-1g-1提高到73.1μmol h-1g-1,是P25的8.9倍。
其次,利用溶剂热法制备了氮掺杂的二氧化钛与石墨烯的杂化材料NTG。以乙二胺为氮源,从商业P25制备了氮掺杂二氧化钛NT,再以NT和GO为原料由水热法制备了NTG。XPS分析结果表明二氧化钛与石墨烯之间存在化学键Ti-C的连接。N的含量是1.43at.%。通过紫外漫反射得出NTG的带隙降低到2.69eV。光吸收拓展到可见光区增强了杂化材料光催化制氢的效率。通过荧光光谱分析证实激发电子从二氧化钛的导带转移到作为电子库的石墨烯。在紫外光照射下,P25、NT、TG和NTG的制氢效率分别为76.1、270.0、370.2和716.0μmol h-1g-1, NTG的光催化效率是P25的9.2倍。在可见光照射下,光催化制氢效率分别为8.2、41.0、57.8和112.0μmol h-1g-1, NTG的光催化效率是P25的13.6倍。
在NTG的基础上,为了进一步提高光催化剂的效率,从P25、乙二胺和氮掺杂石墨烯(NG)通过溶剂热方法制备了氮掺杂二氧化钛与氮掺杂石墨烯的杂化材料NTNG。由氮化锂与四氯化碳溶剂热反应制备了NG。通过XPS分析,NTNG中N的含量是8.6at.%,而NG的N含量是3.5at.%；从NTNG中C1s的高分辨信号上看出Ti-C化学键的形成。石墨烯的N掺杂及Ti-C键接对进一步增强NTNG的光吸收性能均做出了贡献。荧光光谱分析中的荧光猝灭表明NT和NG之间存在相互作用。NG的快速电子转移过程避免了光催化剂光生电子和空穴的复合。电负性较高的N原子具有孤对电子,与石墨烯片层的碳结合成键,改变了邻近碳原子的自旋密度,诱导出更高的载流子密度成为光催化制氢的活性点。紫外光照射下,NTNG的光催化制氢效率为996.8μmol h-1g-1,是P25的13.1倍。
最后,利用有机染料在可见光区吸收性较强的特点拓宽杂化材料的光吸收性能。以曙红(EY)、P25和GO为起始原料,制备了染料敏化的二氧化钛与石墨烯杂化材料T-G-EY。通过紫外可见漫反射结果中明显看出,该材料在400-600nm处有强吸收,其带隙是2.75eV。在T-G-EY的荧光光谱中,观察到了荧光猝灭,证明成分间存在相互作用。在500W氙灯照射下T-G-EY的光催化制氢效率为84.2μmol h-1g-1,是P25的10.2倍。
本论文的研究结果表明,利用石墨烯及其衍生物与二氧化钛的结合方式能不同程度地提高光催化剂光催化分解水制氢的活性。活性的提高归因于石墨烯的存在使得光生载流子快速分离、抑制其在光催化剂体表或者体内的复合。氮掺杂拓宽了光吸收的范围,同时诱导产生具有更高载流子浓度的活性区域,更利于还原甲醇水溶液中质子。这些因素在光催化分解水制氢的过程中起到了协同作用。
Driven by the increase in energy needs and the gradually decrease in fossil fuel resources, and also the environmental concerns of nuclear energy, clean and renewable alternative energy recourses are highly demanded. Hydrogen energy has been regarded as one of the potential energy alternatives to simultaneously address energy and environmental problems because of its environmental friendliness. Several challenges are encountered associated with the hydrogen production, storage, transportation and application. Conversion of fossil fuel resources is the most widely adopted method currently for hydrogen to production, which therefore can not fulfill the requirement of low carbon economy as a consequence of our fossil fuel-based energy system. Photocatalytic hydrogen production from water splitting via semiconductor nanomaterials has long been considered the ultimate solution as an alternative route for solar energy utilization.
Titanium dioxide (T1O2) has been extensively studied and is highlighted as an important semiconductor photocatalyst due to the superior characteristics such as exceptional optoelectronic properties, strong oxidizing power, chemical stability, low cost, and so on. The catalytic efficiency in photocatalytic hydrogen generation is altered by the light absorption ability, the energy levels, the conversion processes of photogenerated charges including generation, recombination, separation, migration and trapping. The wide band gap of TiO2(3.2eV) leads to a low utilization efficiency of sunlight because only the ultraviolet light can meet the energy requirement of electron excitation from the valence band to the conduction band, which hinders the practical application of TiO2in photocatalysis. To extend the light absorption of TiO2, several strategies have been adopted such as the morphology modification, the doping of cation/anion and nonmetal elements (C, N, S, P, etc).
On the other hand, graphene and its derivatives have been regarded as an important component for various functional composite materials owing to its intriguing properties such as superior mobility of charge carriers at room temperature (>200000cm2V-1s-1). Researches about graphene-based semiconductor photocatalysts, including TiO2/graphene nanocomposites, have recently made much rapid progress in the design and fabrication. It has been demonstrated that graphene retards the charge recombination, accelerates the electron transfer and improves the photocatalytic efficiency of hydrogen evolution from water-splitting. Currently, the development of visible-light-driven, stable and highly efficient photocatalysts is very crucial to large-scale hydrogen evolution utilizing solar energy.
In order to obtain a desired performance, the present dissertation discusses the fabrication of a series of nanocomposites composed of titania with graphene&its derivatives. The nanocomposites were fabricated via different approaches, including the nitrogen doping of TiO2, the nitrogen doping of graphene, or an organic dye doping in enhancing the photocatalytic efficiency. These hybrids were characterized with Fourier transform infrared spectra (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), and photoluminescent spectrometry, etc. The photocatalytic activity was evaluated by measuring the hydrogen evolution amount from the methanol aqueous solution by an on-lined gas chromatography (GC).
Firstly, graphene oxide (GO) was prepared from graphite by Hummers'method. The obtained GO sheets contain hydroxyl and carboxyl functional groups on basal planes which allows GO to show a good dispersability in aqueous media, while the electric conductibility of GO is poor because of a mass of non-conjugated defects. Interestingly, the partial ion of conjugated structure in GO could be reconstructed by the reduction via sodium borohydride. TRG-COOH nanocomposites were prepared through simply blending TiO2with the partial reduced GO (RG-COOH), which has a red-shifted band gap of2.80eV as compared with that of P25(3.25eV). TRG-COOH nanocomposite showed a much improved photocatalytic activity under irradiation using500W Xenon lamp with a hydrogen evolution of73.1μmol·h-1·g-1as compared with that of P25(8.2μmol·h-1·g-1), which was increased about8.9times.
Further, nanocomposites of N-doped TiO2with graphene oxide (NTG) were successfully prepared by hydrothermal process from GO and N-doped TiO2(NT) that was prepared via a solvothermal method from commercial P25with1,2-diaminoethane as a nitrogen resource. XPS spectra demonstrated the formation of Ti-C bond between TiO2and graphene. The as-prepared TNG has1.43%N atom, which showed a red-shifted band gap of2.69eV as measured from UV-vis diffuse reflectance spectroscopy. The extending of light absorption to the visible light region would enhance the photocatalytic activity for hydrogen evolution. The excited electrons would mostly transfer to graphene sheets as electron sinks, which was justified by the compared photoluminescence measurements of P25, NT, TG and NTG. UV light irradiation affords P25, NT, TG and NTG a photocatalytic efficiency of76.1,270.0,370.2and716.0μmol h-1g-1, respectively, which is to say that the photocatalytic efficiency of NTG was increased about9.2times as that of P25. The visible light irradiation under Xenon lamp produces a photocatalytic efficiency of8.2,41.0,57.8and112.0μmol·h-1·g-1for P25, NT, TG and NTG, respectively showing about a13.6times activity increase of NTG compared to P25.
In order to further enhance the photocatalytic efficiency, nanocomposites of nitrogen-doped TiO2and nitrogen-doped graphene (NTNG) were prepared via solvothermal method from P25,1,2-diaminoethane and N-doped graphene. N-doped graphene was obtained via mixing lithium nitride (Li3N) with tetrachloromethane (CCl4) through solvothermal approach. The nitrogen content in NTNG was measured as8.6atom%which is much higher than that of NG (3.5atom%) from XPS analysis. The formation of C-Ti bond between TiO2and NG was demonstrated from the high resolution Cls XPS spectra of NTNG, which endowed a enhanced of light absorption. The observed photoluminescent quenching indicated that a strong interaction between the excited state of NT and NG, the fast electron-transportation process avoids the recombination of photo-generated charges, either the electron or the holes. The electronegative N atom with lone electron pair bonding with C atoms in the graphene sheet would change the spin density and induce a higher charge density for the active sites. The UV light irradiation endows P25, NT and NTNG a photocatalytic efficiency of76.1,270.0and996.8μmol·h-1·g-1, respectively showing that the photocatalytic efficiency of NTNG was increased about13.1times as that of P25.
Finally, eosin Y (EY) dye sensitized nanocomposite of TiO2with graphene (T-G-EY) were prepared by hydrothermal process starting from EY, TiO2(P25) and graphene oxide (GO). T-G-EY showed a narrower band gap of2.75eV and a very strong absorption in the visible region of400-600nm from the UV-vis diffuse reflectance absorption spectra. Photoluminescent quenching was also observed, illustrating the interactions between each component in the nanocomposite. The photocatalytic efficiency of T-G-EY for hydrogen evolution from methanol aqueous solution under a500W Xenon lamp irradiation was measured as84.2μmolh-1g-1.
The proposed strategy in this dissertation by the incorporation of graphene&its derivatives with titania enhanced effectively the photocatalytic activity in various degree. TiO2/graphene nanocomposites showed an enhanced photocatalytic activity, which is attributed to the narrowing of band gap and the enhancement of light absorption, the fast separation of photo-generated electron-hole pairs and the retardation of the bulk or surface recombination of photo-induced charges derived from the superior mobility of charge carriers. Nitrogen doping extended the light absorption region further and induced the active region with higher charge density for the reduction of proton in methanol aqueous solution. Improvement in the photocatalytic efficiency for hydrogen evolution is attributed to the synergistic effect of each components in the nanocomposites.
为了实现有效地光催化分解水制氢,研究者对半导体光催化剂进行了广泛的探索。二氧化钛被认为是一种重要的光催化剂,具有优异的光电性能、化学稳定性、低成本等优点。催化剂的光吸收能力、能级水平及光生载流子的转换过程,包括光生载流子的产生、复合、分离、迁移和捕获等,都影响光催化制氢的效率。3.2eV的宽带隙导致二氧化钛对太阳光的利用率低,在很大程度上限制了二氧化钛在光催化方面的应用。为了拓展二氧化钛的光吸收范围,形态修饰、非金属元素(C、N、S、P等)的掺杂等是普遍采用的措施。
另一方面,石墨烯是一种性能优异的碳材料,在室温下具有较高的载流子迁移率(>200000cm2V-1s-1)。基于石墨烯的半导体杂化材料研究取得了很大的进展,其中包括二氧化钛与石墨烯的杂化材料。已有报道表明石墨烯可阻止载流子的复合、促进电荷的转移并提高光催化分解水制氢的效率。
为获得可见光驱动的、稳定和高效的光催化剂用于太阳能光催化分解水制氢,本论文从二氧化钛的氮掺杂、石墨烯的改性、引入染料作为光敏剂三个方面着手,或者这几个方面的综合应用,制备了一系列二氧化钛与石墨烯的杂化材料。分别利用红外光谱(FTIR)、X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、拉曼光谱、原子力显微镜(AFM)、X射线光电子能(XPS)等手段对所制备材料进行了表征。以甲醇水溶液作为光催化产氢体系,通过在线气相色谱仪检测评价了这些材料的光催化活性。
首先,利用Hummers方法从石墨制备石墨氧化物(GO)。GO含有羟基、羧基等含氧官能团,具有很高的水溶性。通过硼氢化钠还原,GO中的共轭结构得到了重建,该产物称之为酸化石墨烯(RG-COOH)=P25与RG-COOH混合得到二氧化钛与酸化石墨烯的杂化材料TRG-COOH.结果证明,由于RG-COOH的引入,杂化材料的带隙从P25的3.25eV降低到2.80eV。TRG-COOH的光催化制氢效率从P25的8.2μmol h-1g-1提高到73.1μmol h-1g-1,是P25的8.9倍。
其次,利用溶剂热法制备了氮掺杂的二氧化钛与石墨烯的杂化材料NTG。以乙二胺为氮源,从商业P25制备了氮掺杂二氧化钛NT,再以NT和GO为原料由水热法制备了NTG。XPS分析结果表明二氧化钛与石墨烯之间存在化学键Ti-C的连接。N的含量是1.43at.%。通过紫外漫反射得出NTG的带隙降低到2.69eV。光吸收拓展到可见光区增强了杂化材料光催化制氢的效率。通过荧光光谱分析证实激发电子从二氧化钛的导带转移到作为电子库的石墨烯。在紫外光照射下,P25、NT、TG和NTG的制氢效率分别为76.1、270.0、370.2和716.0μmol h-1g-1, NTG的光催化效率是P25的9.2倍。在可见光照射下,光催化制氢效率分别为8.2、41.0、57.8和112.0μmol h-1g-1, NTG的光催化效率是P25的13.6倍。
在NTG的基础上,为了进一步提高光催化剂的效率,从P25、乙二胺和氮掺杂石墨烯(NG)通过溶剂热方法制备了氮掺杂二氧化钛与氮掺杂石墨烯的杂化材料NTNG。由氮化锂与四氯化碳溶剂热反应制备了NG。通过XPS分析,NTNG中N的含量是8.6at.%,而NG的N含量是3.5at.%；从NTNG中C1s的高分辨信号上看出Ti-C化学键的形成。石墨烯的N掺杂及Ti-C键接对进一步增强NTNG的光吸收性能均做出了贡献。荧光光谱分析中的荧光猝灭表明NT和NG之间存在相互作用。NG的快速电子转移过程避免了光催化剂光生电子和空穴的复合。电负性较高的N原子具有孤对电子,与石墨烯片层的碳结合成键,改变了邻近碳原子的自旋密度,诱导出更高的载流子密度成为光催化制氢的活性点。紫外光照射下,NTNG的光催化制氢效率为996.8μmol h-1g-1,是P25的13.1倍。
最后,利用有机染料在可见光区吸收性较强的特点拓宽杂化材料的光吸收性能。以曙红(EY)、P25和GO为起始原料,制备了染料敏化的二氧化钛与石墨烯杂化材料T-G-EY。通过紫外可见漫反射结果中明显看出,该材料在400-600nm处有强吸收,其带隙是2.75eV。在T-G-EY的荧光光谱中,观察到了荧光猝灭,证明成分间存在相互作用。在500W氙灯照射下T-G-EY的光催化制氢效率为84.2μmol h-1g-1,是P25的10.2倍。
本论文的研究结果表明,利用石墨烯及其衍生物与二氧化钛的结合方式能不同程度地提高光催化剂光催化分解水制氢的活性。活性的提高归因于石墨烯的存在使得光生载流子快速分离、抑制其在光催化剂体表或者体内的复合。氮掺杂拓宽了光吸收的范围,同时诱导产生具有更高载流子浓度的活性区域,更利于还原甲醇水溶液中质子。这些因素在光催化分解水制氢的过程中起到了协同作用。
Driven by the increase in energy needs and the gradually decrease in fossil fuel resources, and also the environmental concerns of nuclear energy, clean and renewable alternative energy recourses are highly demanded. Hydrogen energy has been regarded as one of the potential energy alternatives to simultaneously address energy and environmental problems because of its environmental friendliness. Several challenges are encountered associated with the hydrogen production, storage, transportation and application. Conversion of fossil fuel resources is the most widely adopted method currently for hydrogen to production, which therefore can not fulfill the requirement of low carbon economy as a consequence of our fossil fuel-based energy system. Photocatalytic hydrogen production from water splitting via semiconductor nanomaterials has long been considered the ultimate solution as an alternative route for solar energy utilization.
Titanium dioxide (T1O2) has been extensively studied and is highlighted as an important semiconductor photocatalyst due to the superior characteristics such as exceptional optoelectronic properties, strong oxidizing power, chemical stability, low cost, and so on. The catalytic efficiency in photocatalytic hydrogen generation is altered by the light absorption ability, the energy levels, the conversion processes of photogenerated charges including generation, recombination, separation, migration and trapping. The wide band gap of TiO2(3.2eV) leads to a low utilization efficiency of sunlight because only the ultraviolet light can meet the energy requirement of electron excitation from the valence band to the conduction band, which hinders the practical application of TiO2in photocatalysis. To extend the light absorption of TiO2, several strategies have been adopted such as the morphology modification, the doping of cation/anion and nonmetal elements (C, N, S, P, etc).
On the other hand, graphene and its derivatives have been regarded as an important component for various functional composite materials owing to its intriguing properties such as superior mobility of charge carriers at room temperature (>200000cm2V-1s-1). Researches about graphene-based semiconductor photocatalysts, including TiO2/graphene nanocomposites, have recently made much rapid progress in the design and fabrication. It has been demonstrated that graphene retards the charge recombination, accelerates the electron transfer and improves the photocatalytic efficiency of hydrogen evolution from water-splitting. Currently, the development of visible-light-driven, stable and highly efficient photocatalysts is very crucial to large-scale hydrogen evolution utilizing solar energy.
In order to obtain a desired performance, the present dissertation discusses the fabrication of a series of nanocomposites composed of titania with graphene&its derivatives. The nanocomposites were fabricated via different approaches, including the nitrogen doping of TiO2, the nitrogen doping of graphene, or an organic dye doping in enhancing the photocatalytic efficiency. These hybrids were characterized with Fourier transform infrared spectra (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), and photoluminescent spectrometry, etc. The photocatalytic activity was evaluated by measuring the hydrogen evolution amount from the methanol aqueous solution by an on-lined gas chromatography (GC).
Firstly, graphene oxide (GO) was prepared from graphite by Hummers'method. The obtained GO sheets contain hydroxyl and carboxyl functional groups on basal planes which allows GO to show a good dispersability in aqueous media, while the electric conductibility of GO is poor because of a mass of non-conjugated defects. Interestingly, the partial ion of conjugated structure in GO could be reconstructed by the reduction via sodium borohydride. TRG-COOH nanocomposites were prepared through simply blending TiO2with the partial reduced GO (RG-COOH), which has a red-shifted band gap of2.80eV as compared with that of P25(3.25eV). TRG-COOH nanocomposite showed a much improved photocatalytic activity under irradiation using500W Xenon lamp with a hydrogen evolution of73.1μmol·h-1·g-1as compared with that of P25(8.2μmol·h-1·g-1), which was increased about8.9times.
Further, nanocomposites of N-doped TiO2with graphene oxide (NTG) were successfully prepared by hydrothermal process from GO and N-doped TiO2(NT) that was prepared via a solvothermal method from commercial P25with1,2-diaminoethane as a nitrogen resource. XPS spectra demonstrated the formation of Ti-C bond between TiO2and graphene. The as-prepared TNG has1.43%N atom, which showed a red-shifted band gap of2.69eV as measured from UV-vis diffuse reflectance spectroscopy. The extending of light absorption to the visible light region would enhance the photocatalytic activity for hydrogen evolution. The excited electrons would mostly transfer to graphene sheets as electron sinks, which was justified by the compared photoluminescence measurements of P25, NT, TG and NTG. UV light irradiation affords P25, NT, TG and NTG a photocatalytic efficiency of76.1,270.0,370.2and716.0μmol h-1g-1, respectively, which is to say that the photocatalytic efficiency of NTG was increased about9.2times as that of P25. The visible light irradiation under Xenon lamp produces a photocatalytic efficiency of8.2,41.0,57.8and112.0μmol·h-1·g-1for P25, NT, TG and NTG, respectively showing about a13.6times activity increase of NTG compared to P25.
In order to further enhance the photocatalytic efficiency, nanocomposites of nitrogen-doped TiO2and nitrogen-doped graphene (NTNG) were prepared via solvothermal method from P25,1,2-diaminoethane and N-doped graphene. N-doped graphene was obtained via mixing lithium nitride (Li3N) with tetrachloromethane (CCl4) through solvothermal approach. The nitrogen content in NTNG was measured as8.6atom%which is much higher than that of NG (3.5atom%) from XPS analysis. The formation of C-Ti bond between TiO2and NG was demonstrated from the high resolution Cls XPS spectra of NTNG, which endowed a enhanced of light absorption. The observed photoluminescent quenching indicated that a strong interaction between the excited state of NT and NG, the fast electron-transportation process avoids the recombination of photo-generated charges, either the electron or the holes. The electronegative N atom with lone electron pair bonding with C atoms in the graphene sheet would change the spin density and induce a higher charge density for the active sites. The UV light irradiation endows P25, NT and NTNG a photocatalytic efficiency of76.1,270.0and996.8μmol·h-1·g-1, respectively showing that the photocatalytic efficiency of NTNG was increased about13.1times as that of P25.
Finally, eosin Y (EY) dye sensitized nanocomposite of TiO2with graphene (T-G-EY) were prepared by hydrothermal process starting from EY, TiO2(P25) and graphene oxide (GO). T-G-EY showed a narrower band gap of2.75eV and a very strong absorption in the visible region of400-600nm from the UV-vis diffuse reflectance absorption spectra. Photoluminescent quenching was also observed, illustrating the interactions between each component in the nanocomposite. The photocatalytic efficiency of T-G-EY for hydrogen evolution from methanol aqueous solution under a500W Xenon lamp irradiation was measured as84.2μmolh-1g-1.
The proposed strategy in this dissertation by the incorporation of graphene&its derivatives with titania enhanced effectively the photocatalytic activity in various degree. TiO2/graphene nanocomposites showed an enhanced photocatalytic activity, which is attributed to the narrowing of band gap and the enhancement of light absorption, the fast separation of photo-generated electron-hole pairs and the retardation of the bulk or surface recombination of photo-induced charges derived from the superior mobility of charge carriers. Nitrogen doping extended the light absorption region further and induced the active region with higher charge density for the reduction of proton in methanol aqueous solution. Improvement in the photocatalytic efficiency for hydrogen evolution is attributed to the synergistic effect of each components in the nanocomposites.
引文
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