CN108940252A - 一种氧化锌/碳复合光催化纳米材料及其制备方法 - Google Patents
一种氧化锌/碳复合光催化纳米材料及其制备方法 Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 15
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011701 zinc Substances 0.000 claims abstract description 16
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 16
- 150000007524 organic acids Chemical class 0.000 claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011746 zinc citrate Substances 0.000 claims description 2
- 229940068475 zinc citrate Drugs 0.000 claims description 2
- 235000006076 zinc citrate Nutrition 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 239000005416 organic matter Substances 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 description 8
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
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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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
本发明公开了一种氧化锌/碳复合光催化纳米材料，由多孔碳层负载氧化锌纳米粒子构成，所述的氧化锌纳米颗粒的粒径为5～10nm。其制备方法为，以有机酸锌为前驱体，在氮气气氛中高温煅烧而成。制备过程简单，环境友好，所得材料光生电子‑空穴复合效率低，光催化活性高，易于回收利用，在含有机物污水处理方面具有广阔的应用前景。
Description
技术领域
本发明涉及一种氧化锌/碳复合光催化纳米材料的制备方法，属 于氧化物半导体复合光催化材料制备领域。
背景技术
随着社会发展,能源短缺与环境污染已经成为人们关注的焦点问 题。光催化技术，作为一种绿色高级氧化技术，在环境污染治理领域 和能源转化方面有着广泛的应用前景。光催化技术能够将低密度的太 阳能转化成高密度易存储的氢能，从而解决能源短缺问题；能够把有 毒有害的有机、无机环境污染物降解或矿化成低毒、无毒的物质，减 少环境污染。
氧化锌是一种重要的半导体光催化材料，具有稳定性高、成本低、 无毒性等优点。但是氧化锌的禁带宽度为3.37eV，易于光腐蚀，光 利用率低，且光生电子-空穴的复合速率高，因此量子效率较低。碳 材料是一种惰性材料，由于其良好的导电性，能够捕捉和传输电子。 将氧化锌和碳材料进行复合，可以提高光催剂抗光腐蚀能力；加快半 导体内光生电子和空穴的分离，抑制载流子复合以提高量子产率；扩 大光吸收的范围，增加对光的利用率，使得氧化锌基光催化材料有更 加广发的实际应用前景。
发明内容
为解决现有技术中半导体光催化材料氧化锌的禁带宽度为 3.37eV，易于光腐蚀，光利用率低，且光生电子-空穴的复合速率高， 量子效率较低的缺陷，本发明提供一种氧化锌/碳复合光催化纳米材 料及其制备方法。
一种氧化锌/碳复合光催化纳米材料，由多孔碳层负载氧化锌纳 米粒子构成，所述的氧化锌纳米颗粒的粒径为5～10nm。通过以有机 酸锌为前驱体，在氮气气氛中高温煅烧而成。
进一步的，将有机酸锌前驱体装于石英舟中，将石英舟置于管式 炉中，持续通入氮气，管式炉升温速率为5～10℃/min，温度升至 500～650℃后保温煅烧3～5h，即得。优选的，有机酸锌前驱体为醋 酸锌、草酸锌和柠檬酸锌中的任意一种或多种。
有益效果：本发明的通过简单易行的方法合成出了氧化锌/碳复 合光催化纳米材料，该光催化纳米材料由多孔碳层负载氧化锌纳米粒 子构成。该材料光生电子-空穴复合效率低，光催化活性高，易于回 收利用。
有机酸锌前驱体不仅提供了氧化锌基，同时提供了碳源；碳层作 为氧化锌纳米粒子的载体，控制了其形成较小的纳米尺寸，提高了其 分散性。氧化锌-碳层异质结界面的形成，提高了催化剂的稳定性， 提高了光吸收范围和强度，同时有利于催化剂光生电子-空穴的分离， 协同提高了光催化材料的活性。反应结束后，催化剂在水中沉降性好， 易与水分离，易于回收利用。
附图说明
附图用来提供对本发明的进一步理解，并且构成说明书的一部分， 与本发明的实施例一起用于解释本发明，并不构成对本发明的限制。 在附图中：
图1为氧化锌/碳复合光催化材料的透射电子显微镜照片；
图2为氧化锌/碳复合光催化材料的XRD衍射图谱；
图3为氧化锌/碳复合光催化材料的光致发光图谱。
具体实施方式
以下对本发明的优选实施例进行说明，应当理解，此处所描述的 优选实施例仅用于说明和解释本发明，并不用于限定本发明。
实施例1：
0.5g有机酸锌前驱体装于石英舟中，将石英舟置于管式炉中， 持续通入氮气，管式炉升温速率为10℃/min，温度升至550℃，在此 温度下煅烧4h，制得氧化锌/碳复合光催化纳米材料。
通过UV-3600紫外-可见光分光光度计测量，该光催化纳米材料 在光照25min后对亚甲基蓝的降解率为99.7％。
实施例2：
0.5g有机酸锌前驱体装于石英舟中，将石英舟置于管式炉中， 持续通入氮气，管式炉升温速率为5℃/min，温度升至650℃，在此 温度下煅烧3h，制得氧化锌/碳复合光催化纳米材料。
通过UV-3600紫外-可见光分光光度计测量，该光催化纳米材料 在光照25min后对亚甲基蓝的降解率为99.0％。
实施例3：
0.5g有机酸锌前驱体装于石英舟中，将石英舟置于管式炉中， 持续通入氮气，管式炉升温速率为8℃/min，温度升至500℃，在此 温度下煅烧5h，制得氧化锌/碳复合光催化纳米材料。
通过UV-3600紫外-可见光分光光度计测量，该光催化纳米材料 在光照25min后对亚甲基蓝的降解率为98.6％。
最后应说明的是：以上所述仅为本发明的优选实施例而已，并不 用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明， 对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技 术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发 明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包 含在本发明的保护范围之内。
Claims (4)
1.一种氧化锌/碳复合光催化纳米材料，其特征在于，由多孔碳层负载氧化锌纳米粒子构成，所述的氧化锌纳米颗粒的粒径为5～10nm。
2.一种权利要求1所述的氧化锌/碳复合光催化纳米材料的制备方法，其特征在于，以有机酸锌为前驱体，在氮气气氛中高温煅烧而成。
3.如权利要求2所述的制备方法，其特征在于，将有机酸锌前驱体装于石英舟中，将石英舟置于管式炉中，持续通入氮气，管式炉升温速率为5～10℃/min，温度升至500～650℃后保温煅烧3～5h，即得。
4.根据权利要求3所述的制备方法，其特征在于，所述有机酸锌前驱体为醋酸锌、草酸锌和柠檬酸锌中的任意一种或多种。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109809387A (zh) * | 2019-04-15 | 2019-05-28 | 山东大学 | 一种多孔碳材料及其制备方法 |
| US11472715B2 (en) | 2020-10-23 | 2022-10-18 | King Faisal University | Method of making carbon-zinc oxide nanoparticles |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109809387A (zh) * | 2019-04-15 | 2019-05-28 | 山东大学 | 一种多孔碳材料及其制备方法 |
| US11472715B2 (en) | 2020-10-23 | 2022-10-18 | King Faisal University | Method of making carbon-zinc oxide nanoparticles |
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Application publication date: 20181207 |