CN106622331B - 一种高比表面积石墨相氮化碳光催化剂的制备方法 - Google Patents
一种高比表面积石墨相氮化碳光催化剂的制备方法 Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/39—Photocatalytic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/613—10-100 m2/g
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
Abstract
本发明公开了一种高比表面积石墨相氮化碳光催化剂的制备方法。该方法包括如下步骤:(1)将尿素经机械力研磨处理得到均匀细小固体颗粒;(2)将所得产物置于加盖坩埚内,在空气氛围下马弗炉中进行煅烧、恒温、自然冷却处理,即得所述高比表面积石墨相氮化碳光催化剂。本发明提供的高比表面积石墨相氮化碳光催化剂的制备方法其原料价廉、成本低、绿色无污染,操作方便、简单易控,有效地提高了石墨相氮化碳的比表面积,具有良好的应用前景和潜在实用价值。
Description
技术领域
本发明涉及光催化材料技术领域,特别涉及一种高比表面积石墨相氮化碳光催化剂的制备方法。
背景技术
石墨相氮化碳是一种类石墨结构的聚合物半导体,其禁带宽度约为2.7eV,可以吸收太阳光谱中波长小于475nm的蓝紫光,即在可见光区有吸收。由于其具有稳定性高、独特的电子能带结构、廉价、无毒等优点,石墨相氮化碳被作为新型非金属光催化剂广泛应用于环境污染及各类催化反应中,如光分解水产氢、降解有机污染物等。众所周知,光催化剂表面结构对于光催化活性有着至关重要的作用,比表面积的增大有利于半导体光生载流子的分离,可以使光催化性能大幅度增强。
本发明制备出的石墨相氮化碳与已有文献 [Jinghai Liu, Yuewei Zhang,Luhua Lu, Guan Wu and Wei Chen. Self-regenerated solar-driven photocatalyticwater-splitting by urea derived graphitic carbon nitride with platinumnanoparticles. Chem. Common., 2012, 48, 8826-8828.]和 [Yuewei Zhang, JinghaiLiu, Guan Wu and Wei Chen. Porous graphitic carbon nitride synthesized viadirect polymerization of urea for efficient sunlight-driven photocatalytichydrogen production. Nanoscale, 2012, 4, 5300-5303.] 报道的直接以尿素为原料制备的石墨相氮化碳比表面积增大了28.04~52.08m2/g。通过简单、绿色的机械力研磨处理原料,再进行煅烧制备多孔、高比表面积的石墨相氮化碳光催化剂材料还未见相关报道。
发明内容
本发明的目的是提供一种高比表面积石墨相氮化碳光催化剂的制备方法,该方法使用机械力研磨处理原料,可以有效提高石墨相氮化碳的比表面积,操作简单易行、绿色无污染。
本发明提供的一种高比表面积石墨相氮化碳光催化剂的制备方法,包括如下具体步骤:
(1)称取尿素置于直径12cm玻璃研钵,使用研磨棒用力画圈研磨,至原料呈均匀细小的固体粉末状;
(2)将(1)研磨过的尿素原料置于加盖坩埚中,空气氛围下在马弗炉中分段进行煅烧、恒温、自然冷却处理,即得高比表面积石墨相氮化碳光催化剂。
上述制备方法中,步骤(1)中尿素质量为10~30g,具体可为10g、20g、30g;研磨时间范围为2~4h,研磨速度为40~60圈/分钟。
上述制备方法中,步骤(2)在空气氛围下,马弗炉分段进行加热升温、恒温及自然冷却处理,其中马弗炉升温速率为11~20℃/min,具体可为16℃/min;加热温度设置为350~600℃,具体可分别设为400和550℃;加热恒温总时间为4h~6h,具体可将两个温度段分别设置为2h。
本发明提供了上述方法制备的高比表面积石墨相氮化碳光催化材料的部分表征,所述石墨相氮化碳光催化剂的比表面积为97.64~121.68m2/g,平均孔径为18.97~44.51nm。
本发明提供的高比表面积石墨相氮化碳既是一种非金属半导体光催化剂,又是一种良好的载体。本发明提供的高比表面积石墨相氮化碳光催化剂的制备方法,其原料廉价、工艺简单、绿色无毒,具有很高的应用前景和实用价值。
附图说明
图1为实施例1制备的高比表面积石墨相氮化碳的SEM图。
表1为实施例1和2制备的高比表面积石墨相氮化碳与文献石墨相氮化碳的孔径分布表。
图2为实施例1和2制备的高比表面积石墨相氮化碳与常规石墨相氮化碳的XRD图。
具体实施方式
本发明下述实施例中所使用的实验方法如无特殊说明,均为常规方法。
本发明下述实施例中所使用的材料、试剂等,如无特殊说明,均可从商业途径得到。
本发明下述实施例中所使用的初始反应物为市售分析纯的尿素。
本发明下述实施例中,采用日本理学株式会社MiniFlex 600型X射线衍射仪(XRD)( Cu Kα射线,λ=1.5406Å,电压为40kV,电流为30mA)测试所制备石墨相氮化碳的晶型结构;采用美国Micromeritics ASAP 2020型全自动化学吸附仪测定所制备石墨相氮化碳的比表面积(BET)和孔分布;采用德国卡尔蔡司 SUPRA 55 Sapphire型场发射扫描电子显微镜(FE-SEM)测试所制备石墨相氮化碳的形貌。
实施例1
称取30g尿素于直径12cm的玻璃研钵中,使用研磨棒用力画圈研磨2h(平均50圈/分钟),至原料呈均匀细小的固体粉末状;将研磨好的尿素产物置于100mL陶瓷坩埚(加盖),放入马弗炉中在空气氛围下开始加热升温,加热参数设置如下:由室温25~30℃升温至400℃,升温速率为16℃/min,在400℃下恒温2h;然后加热升温至550℃,升温速率为16℃/min,在550℃下恒温2h;自然冷却至室温25~30℃。将得到的淡黄色固体研磨,即得到高比表面积石墨相氮化碳光催化剂材料。
如图1所示,本发明实施制备的石墨相氮化碳具有很多孔洞结构,属于多孔材料。
实施例2
称取25g尿素于直径12cm的玻璃研钵中,使用研磨棒用力画圈研磨4h(平均50圈/分钟),至原料呈均匀细小的固体粉末状;将研磨好的尿素产物置于100mL陶瓷坩埚(加盖),放入马弗炉中在空气氛围下开始加热升温,加热参数设置如下:由室温25~30℃升温至400℃,升温速率为15℃/min,在400℃下恒温2h;然后加热升温至550℃,升温速率为15℃/min,在550℃下恒温2h;自然冷却至室温25~30℃。将得到的淡黄色固体研磨,即得到高比表面积石墨相氮化碳光催化剂材料。
表1为实施例1和2制备的高比表面积石墨相氮化碳与文献石墨相氮化碳的孔径分布表。
由表1中的数据可得知,尿素原料经过机械力研磨处理后制备的石墨相氮化碳比表面积得到显著的提高。
如图2所示,本发明实施例1、2制备的高比表面积石墨相氮化碳结晶度良好,2θ为13.2°和27.5°分别对应石墨相氮化碳的(100)和(002)晶面。
Claims (1)
1.一种高比表面积石墨相氮化碳光催化剂的制备方法,其特征包括如下步骤:
(1)尿素原料经过机械力研磨处理:在玻璃研钵中加入原料,使用研磨棒用力画圈研磨2~4小时,研磨速度为每分钟40~60圈,形成均匀细小的原料粉末;
(2)将(1)研磨后的尿素置于加盖坩埚,在马弗炉中分两段进行煅烧、恒温,最终自然冷却至室温25~30℃,即获得高比表面积石墨相氮化碳光催化剂;其中煅烧温度设置分别为400和550℃;升温速率为11~16℃/min,将两个温度段加热时间分别设置为2小时。
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CN110560127A (zh) * | 2019-09-09 | 2019-12-13 | 辽宁石油化工大学 | 大比表面积石墨相氮化碳的制备方法 |
CN110759321A (zh) * | 2019-10-23 | 2020-02-07 | 东北大学 | 一种可见光吸收增强石墨相氮化碳材料的制备方法 |
CN110813357B (zh) * | 2019-11-15 | 2023-02-28 | 南宁师范大学 | 高效双孔g-C3N4光催化剂的制备方法 |
CN113736464B (zh) * | 2021-08-23 | 2023-07-18 | 湖北大学 | 稀土上转换纳米颗粒/类石墨相氮化碳复合材料、电池及制备方法 |
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