氧掺杂氮化碳纳米片的制备及其光解水制氢性能
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摘要
以草酸为氧源,二聚氰胺和尿素为原料,采用两步热聚合方式合成氧掺杂氮化碳纳米片催化剂(CNO)。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、紫外-可见吸收光谱(UV-Vis)、X射线光电子能谱分析(XPS)、荧光光谱(PL)及电化学测试等技术对催化剂进行结构表征分析。在可见光照射下通过分解水制氢反应对CNO的光催化还原性能进行评价。结果表明,草酸中的O元素通过取代氮化碳三嗪环结构中N原子直接键合到sp~2杂化碳上,形成O掺杂CNO。经O掺杂改性后的氮化碳具有良好的层状堆积结构,可见光吸收性明显提高,同时禁带宽度降低。O掺杂的引入加速了光生电子-空穴对的分离和传输,能大幅度提高氮化碳的光催化分解水制氢性能,在可见光照下达88.6μmol·h~(-1),是未掺杂CN的3.91倍。
Oxygen-doped carbon nitride nanosheets catalyst(CNO) was synthesized by two-step thermal polymerization method using oxalic acid as oxygen source, melamine and urea as raw materials. X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), ultraviolet-visible absorption spectroscopy(UV-Vis), X-ray photoelectron spectroscopy(XPS), fluorescence spectroscopy(PL), and electrochemical measurements were carried out to characterize and analyze the structures of catalysts. The photocatalytic reduction properties of CNO were tested by H_2 production from water splitting under visible light irradiation. The results showed that O elements directly replaced N in the triazine ring structure and bonded to the sp~2 hybridized carbon to form CNO. The CNO showed good layered structure, improved absorption of visible light, and lowered band gap. Due to the O doping, the separation and transmission of photogenerated electron-hole pairs were accelerated. Under visible light irradiation, the hydrogen generation rate from water by CNO was greatly enhanced and the evolution rate was up to 88.6 μmol·h~(-1), which was 3.91 times as undoped CN.
Oxygen-doped carbon nitride nanosheets catalyst(CNO) was synthesized by two-step thermal polymerization method using oxalic acid as oxygen source, melamine and urea as raw materials. X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), ultraviolet-visible absorption spectroscopy(UV-Vis), X-ray photoelectron spectroscopy(XPS), fluorescence spectroscopy(PL), and electrochemical measurements were carried out to characterize and analyze the structures of catalysts. The photocatalytic reduction properties of CNO were tested by H_2 production from water splitting under visible light irradiation. The results showed that O elements directly replaced N in the triazine ring structure and bonded to the sp~2 hybridized carbon to form CNO. The CNO showed good layered structure, improved absorption of visible light, and lowered band gap. Due to the O doping, the separation and transmission of photogenerated electron-hole pairs were accelerated. Under visible light irradiation, the hydrogen generation rate from water by CNO was greatly enhanced and the evolution rate was up to 88.6 μmol·h~(-1), which was 3.91 times as undoped CN.
引文
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[6] HUANG Tao(黄涛), ZHANG Guo-Liang(张国亮), ZHANG Hui(张慧), et al. Chemical Industry and Engineering Progress(化工进展), 2010,29(3):498-504
[7] ZHANG Jing(张晶), ZHANG Ya-Ping(张亚萍), YU LianQing(于濂清), et al. Inorganic Chemicals Industry(无机盐工业), 2010,42(9):6-9
[8] NI Guang-Hong(倪广红), FENG Ping(丰平). Nanoscience&Technology(纳米科技), 2010,7(2):81-86
[9] ZHANG Ya-Ping(张亚萍), ZHANG An-Yu(张安玉), YU Lian-Qing(于濂清), et al. J. Inorg. Mater.(无机材料学报),2016,31(3):269-272
[10]Cao S, Low J, Yu J, et al. Adv. Mater., 2015,27(13):2150-2176
[11]Liu J H, Xie S Y, Geng Z B, et al. Nano Lett., 2016,16(10):6568-6573
[12]CHEN Yan(陈艳), LIU Hai-Bo(刘海波), et al. Chinese J.Inorg. Chem.(无机化学学报), 2017,33(12):2255-2261
[13]Li X H, Wang X C, Antonietti M, et al. J. Am. Chem. Soc.,2009,131(5):1680-1681
[14]Li X H, Wang X C, Antonietti M, et al. Chem. Sci., 2012,3(6):2170-2174
[15]Yan S C, Li Z S, Zou Z G, et al. Langmuir, 2010,26(6):3894-3901
[16]Liu G, Niu P, Sun C H, et al. J. Am. Chem. Soc., 2010,132(33):11642-11648
[17]Yan D D, Dr X W, Thomas P, et al. ChemCatChem, 2010,2(7):834-838
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[19]Jie F, Chang B B, Tian Y L, et al. J. Mater. Chem. A, 2013,1(9):3083-3090
[20]Ong W J, Tan L L, Ng Y H, et al. Chem. Rev., 2016,116(12):7159-7329
[21]Li J H, Shen B, Hong Z H, et al. Chem. Commun., 2012,48(98):12017-12019
[22]Huang Z F, Song J, Pan L, et al. Nano Energy, 2015,12:646-656
[23]CUI Yan-Juan(崔言娟), WANG Yu-Xiong(王愉雄), WANG Hao(王浩), et al. Chin. J. Catal.(催化学报), 2016,37(11):1899-1906
[24]Rong X S, Qiu F X, Rong J, et al. J. Solid State Chem.,2015,230:126-134
[25]ZHAI Shun-Chen(翟顺成), GUO Pin(郭平), ZHEN Ji-Ming(郑继明), et al. Acta Physica Sinica(物理学报), 2017,66(18):187102
[26]LI Xin(李欣), WANG Tie-Cheng(王铁成), QU Guang-Zhou(屈广州), et al. Chinese Journal of Environmental Engineering(环境工程学报), 2017,11(5):2738-2742
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[29]Li J H, Shen B, Hong Z H, et al. Chem. Commun., 2012,48(98):12017-12019