CN109433246B - 含有碳空位的纳米片c3n4光催化剂及制备方法 - Google Patents
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Abstract
本发明涉及环境能源技术，尤其涉及含有碳空位的纳米片C3N4光催化剂及制备方法，该制备方法为：浓硫酸剥离及热处理制备多孔Cu2‑xSe薄片。本发明用浓硫酸剥离，能够得到薄片状C3N4和氧掺入晶格C3N4中，从而提高光催化性能。通过退火处理，得到含有碳空位的纳米片C3N4。通过可见光激发4小时后，含有碳空位的纳米片C3N4光催化剂能够将水分解为235µmol/g的H2。
Description
技术领域
本发明涉及光催化和化学剥离技术，尤其涉及一种用于光催化分解水制氢的含有碳空位的纳米片C3N4光催化剂及制备方法。
背景技术
随着现代工业的发展，能源短缺越来越严重。光催化分解水制氢，是一种利用太阳能的绿色技术，取之不尽，用之不竭。C3N4具有类似石墨的二维层状结构，带隙为2.7eV，价带顶电位满足氧化水制取氧气的电位要求，而导带底电位满足还原水制取氢气的电位要求，且响应吸收太阳辐射中波长小于475 nm的蓝紫光能量。一些研究工作证实在氨气中处理C3N4产生碳空位能够提高催化效率，但是很危险，且引起环境污染。因此，需要探索新的方法来产生碳空位。
发明内容
针对上述问题，本发明提供一种成本较低、效率高的含有碳空位的纳米片C3N4光催化剂及制备方法。
为达上述发明目的，本发明采用的技术方案为：一种含有碳空位的纳米片C3N4光催化剂，包括有002晶面向小角度偏移、碳空位、EPR信号增强、高的光催化性能。
较佳地，所述的含有碳空位的纳米片C3N4光催化剂，C3N4在空气中退火处理后，002晶面向小角度偏移，降低了晶面间距，促使COO-基团的消失，从而产生碳空位。
较佳地，所述的含有碳空位的纳米片C3N4光催化剂的EPR信号，随着退火温度的提高逐渐增强，表明存在碳空位。
较佳地，所述的含有碳空位的纳米片C3N4光催化剂的光催化分解水制氢的性能，相对于纳米片状的C3N4提高了16倍。
一种含有碳空位的纳米片C3N4光催化剂制备方法，其特征在于：包括以下步骤：
首先将三聚氰胺在550 ℃煅烧 4 小时，随炉冷却到室温，研碎得到黄色粉末C3N4；在室温下将2g黄色C3N4在20 mL of 浓H2SO4磁力搅拌 6 小时，接着缓慢将混合物滴入200mL 去离子水中，随后超声剥离，直到溶液从黄色变为无色；将上述混合溶液用去离子水清洗3次，直到溶液呈中性，随后通过超声分散和冷冻干燥得到纳米片C3N4粉末；将制备的纳米片C3N4粉末加热到600℃并保温1小时，随炉冷却即得到含有碳空位的纳米片C3N4粉末。
本发明含有碳空位的纳米片C3N4光催化剂，用浓硫酸剥离，能够得到薄片状C3N4和氧掺入晶格C3N4中，从而提高光催化性能。通过退火处理，得到含有碳空位的纳米片C3N4。通过可见光激发4小时后，含有碳空位的纳米片C3N4光催化剂能够将水分解为235µmol/g的H2。
附图说明
图1为本发明实施例制备含有碳空位的纳米片C3N4光催化剂的XRD图；
图2为本发明实施例制备含有碳空位的纳米片C3N4光催化剂的EPR信号图；
图3为本发明实施例制备含有碳空位的纳米片C3N4的光催化性能图。
具体实施方式
为更好地理解本发明，下面将结合附图和具体实施方式对本发明的技术方案做进一步说明，参见图1至图3：
一种含有碳空位的纳米片C3N4光催化剂制备方法，其特征在于：包括以下步骤：
首先将三聚氰胺在550 ℃煅烧 4 小时，随炉冷却到室温，研碎得到黄色粉末C3N4；在室温下将2g黄色C3N4在20 mL of 浓H2SO4磁力搅拌 6 小时，接着缓慢将混合物滴入200mL 去离子水中，随后超声剥离，直到溶液从黄色变为无色；将上述混合溶液用去离子水清洗3次，直到溶液呈中性，随后通过超声分散和冷冻干燥得到纳米片C3N4粉末；将制备的纳米片C3N4粉末加热到600℃并保温1小时，随炉冷却即得到含有碳空位的纳米片C3N4粉末。
按本发明实施的含有碳空位的纳米片C3N4光催化剂。图1为本发明实施例制备含有碳空位的纳米片C3N4光催化剂的XRD图，BCN表示块状C3N4，CNS表示纳米片状C3N4，CNS-400、500、600分别表示纳米片状C3N4在400、500、600 ℃退火处理。从图1可看知，随着C3N4从块状变为纳米片状，（002）峰向左偏移，表明通过浓H2SO4处理后，C3N4插入了含氧的功能团。将纳米片状C3N4退火处理后，（002）峰进一步向左偏移，促使COO-基团的消失，从而产生碳空位。
图2为本发明实施例制备含有碳空位的纳米片C3N4光催化剂的EPR信号图。从图1可看知，其信号主要出现在3360-3420，信号强度随着退火温度的提高逐渐增强，表明存在碳空位。
图3为本发明实施例制备含有碳空位的纳米片C3N4的光催化性能图。从图3可以看出，可见光激发4小时后，含有碳空位的纳米片C3N4光催化剂能够将水分解为235µmol/g的H2，相对于纳米片状的C3N4提高了16倍。
Claims (1)
1.一种含有碳空位的纳米片C3N4光催化剂制备方法，其特征在于：包括以下步骤：首先将三聚氰胺在550℃煅烧4小时，随炉冷却到室温，研碎得到黄色粉末C3N4；在室温下将2g黄色C3N4在20mL浓H2SO4中磁力搅拌6小时，接着缓慢将混合物滴入200 mL去离子水中，随后超声剥离，直到溶液从黄色变为无色；将上述混合溶液用去离子水清洗3次，直到溶液呈中性，随后通过超声分散和冷冻干燥得到纳米片C3N4粉末；将制备的纳米片C3N4粉末加热到600℃并保温1小时，随炉冷却即得到含有碳空位的纳米片C3N4粉末。
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| CN104801329A (zh) * | 2015-05-08 | 2015-07-29 | 南昌航空大学 | 一种CdS量子点/超薄g-C3N4纳米片复合光催化剂及其制备方法 |
| CN105195204A (zh) * | 2015-10-19 | 2015-12-30 | 合肥工业大学 | 一种超细g-C3N4纳米光催化剂及其制备方法 |
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| CN108686690A (zh) * | 2017-04-12 | 2018-10-23 | 中国科学院福建物质结构研究所 | 一种基于石墨相氮化碳g-C3N4的光催化剂及其制备方法和应用 |
| CN107486230A (zh) * | 2017-08-10 | 2017-12-19 | 东北大学 | 一种高活性大比表面积纳米片状结构g‑C3N4的制备方法 |
| CN108355702A (zh) * | 2018-03-23 | 2018-08-03 | 辽宁大学 | 一种大比表面积碳缺陷石墨相氮化碳光催化剂及其制备方法和应用 |
| CN108704656A (zh) * | 2018-05-31 | 2018-10-26 | 武汉大学 | 一种表面碳空位修饰的石墨相氮化碳光催化剂的制备方法及其在生产双氧水过程中的应用 |
| CN108772093A (zh) * | 2018-06-27 | 2018-11-09 | 中南民族大学 | 一种高可见光活性石墨相氮化碳纳米片及其制备方法 |
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