CN107051459A - 一种核壳型氧化铜/铜光催化剂的制备方法 - Google Patents
一种核壳型氧化铜/铜光催化剂的制备方法 Download PDFInfo
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229960004643 cupric oxide Drugs 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical class [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims 1
- 239000012279 sodium borohydride Substances 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 5
- 229910052708 sodium Inorganic materials 0.000 abstract description 5
- 239000011734 sodium Substances 0.000 abstract description 5
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- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
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- 238000009416 shuttering Methods 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
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- 238000004042 decolorization Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 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 2
- YYYARFHFWYKNLF-UHFFFAOYSA-N 4-[(2,4-dimethylphenyl)diazenyl]-3-hydroxynaphthalene-2,7-disulfonic acid Chemical compound CC1=CC(C)=CC=C1N=NC1=C(O)C(S(O)(=O)=O)=CC2=CC(S(O)(=O)=O)=CC=C12 YYYARFHFWYKNLF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 238000000034 method Methods 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
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- 239000010842 industrial wastewater Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
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- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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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- 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
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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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- 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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Abstract
本发明公开一种核壳型氧化铜/铜光催化剂的制备方法。依次包括如下步骤：将1～4g十六烷基三甲基溴化铵溶解到20mL甲苯中，加入4～5g过80～100目筛的氧化铜粉末，超声分散20～100min，加入5～20mL水，在400～600转/分钟的转速下加入0.5～1g硼氢化钠，继续搅拌4～8min，沉淀分离，得到一种核壳型氧化铜/铜光催化剂。氧化铜既作为制备铜单质的前驱体又作为载体提供支撑纳米颗粒成核、生长的活性位功能，表面活性剂控制纳米颗粒的生长作为模板功能，向含有支撑‑模板双功能微观反应环境的混合物中加入还原剂，在其表面部分还原，制得内核为氧化铜表面是铜的核壳型催化剂，同时氧化铜/铜之间有协同作用，能更好的促进催化作用。
Description
技术领域
本发明涉及环境污染控制新材料的开发，尤其涉及一种核壳型氧化铜/铜光催化剂的制备方法。
背景技术
在生活污水、食品加工和造纸等工业废水中，含有碳水化合物、蛋白质、油脂、木质素等有机物质。这些物质以悬浮或溶解状态存在于污水中，可通过微生物的生物化学作用而分解。在其分解过程中需要消耗氧气，因而被称为耗氧污染物。这种污染物可造成水中溶解氧减少，影响鱼类和其他水生生物的生长。水中溶解氧耗尽后，有机物进行厌氧分解，产生硫化氢、氨和硫醇等难闻气味，使水质恶化。
随着生产的发展，来自工农业生产中产生的毒害有机污染物严重威胁着环境和人类的健康，寻求一种新型高效的环境治理技术具有重要的意义。光催化技术因其节能、高效、污染物降解彻底、无二次污染优点，目前已成为一种具有重要应用前景的新兴环境治理技术。近年来，新型高效的可见光光催化剂的研制成为光催化技术中的一个重要研究内容。
作为一类p型过渡金属氧化物，氧化铜在电、磁和催化等领域表现出奇特的物理和化学性能，引起人们的广泛关注，被广泛应用于印染、陶瓷、电极活性材料及催化剂等重要领域。氧化铜的物理和化学性能受形貌、尺寸和结构影响。近年来，具有不同形貌结构的氧化铜材料引起人们的极大兴趣，已通过不同方法制备了氧化铜纳米线、纳米棒、纳米片、纳米管、纳米带等。一些更为复杂的结构如花状、蜂窝状、空心球等也有相关报道。核壳型氧化铜有其特别之处，在铜和氧化铜相互协同作用下，可以提高氧化铜的活性。
发明内容
本发明的目的是为克服现有技术中氧化铜结构单一的不足，提供一种核壳型氧化铜/铜光催化剂的制备方法。
本发明采用的技术方案是依次包括如下步骤：
将1～4g十六烷基三甲基溴化铵溶解到20mL甲苯中，加入4～5g过80～100目筛的氧化铜粉末，超声分散20～100min，加入5～20mL水，在400～600转/分钟的转速下加入0.5～1g硼氢化钠，继续搅拌4～8min，沉淀分离，得到一种核壳型氧化铜/铜光催化剂。
本发明的优点是：氧化铜既作为制备铜单质的前驱体又作为载体提供支撑纳米颗粒成核、生长的活性位功能，表面活性剂控制纳米颗粒的生长作为模板功能，向含有支撑-模板双功能微观反应环境的混合物中加入还原剂，在其表面部分还原，制得内核为氧化铜表面是铜的核壳型催化剂，同时氧化铜/铜之间有协同作用，能更好的促进催化作用。
具体实施方式
以下进一步提供本发明的3个实施例：
实施例1
将4g十六烷基三甲基溴化铵溶解到20mL甲苯中，加入5g过100目筛的氧化铜粉末，超声分散100min，加入20mL水，在600转/分钟的转速下加入1g硼氢化钠，继续搅拌8min，沉淀分离，得到一种核壳型氧化铜/铜光催化剂。
将制得的核壳型氧化铜/铜光催化剂用于处理含酸性大红废水：将得到的核壳型氧化铜/铜光催化剂置于待处理50mL浓度为10mg/L的含酸性大红废水中，在300W金卤灯照射下，反应40min，脱色率为95.7％。
实施例2
将1g十六烷基三甲基溴化铵溶解到20mL甲苯中，加入4g过80目筛的氧化铜粉末，超声分散20min，加入5mL水，在400转/分钟的转速下加入0.5g硼氢化钠，继续搅拌4min，沉淀分离，得到一种核壳型氧化铜/铜光催化剂。
将制得的核壳型氧化铜/铜光催化剂用于处理含亚甲基蓝废水：将得到的核壳型氧化铜/铜光催化剂置于待处理50mL浓度为10mg/L的含亚甲基蓝废水中，在300W金卤灯照射下，反应40min，脱色率为95.9％。
实施例3
将3g十六烷基三甲基溴化铵溶解到20mL甲苯中，加入5g过80目筛的氧化铜粉末，超声分散80min，加入10mL水，在600转/分钟的转速下加入0.6g硼氢化钠，继续搅拌8min，沉淀分离，得到一种核壳型氧化铜/铜光催化剂。
将制得的核壳型氧化铜/铜光催化剂用于处理含罗丹明B废水：将得到的核壳型氧化铜/铜光催化剂置于待处理50mL浓度为10mg/L的含罗丹明B废水中，在300W金卤灯照射下，反应40min，脱色率为98.1％。
Claims (1)
1.一种核壳型氧化铜/铜光催化剂的制备方法，其特征是依次包括如下步骤：
将1～4g十六烷基三甲基溴化铵溶解到20mL甲苯中，加入4～5g过80～100目筛的氧化铜粉末，超声分散20～100min，加入5～20mL水，在400～600转/分钟的转速下加入0.5～1g硼氢化钠，继续搅拌4～8min，沉淀分离，得到一种核壳型氧化铜/铜光催化剂。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070181A (zh) * | 2011-01-14 | 2011-05-25 | 浙江大学 | 一种氧化亚铜的制备方法 |
| CN102357659A (zh) * | 2011-07-27 | 2012-02-22 | 西安交通大学 | 一种Cu-Cu2O异质结的制备方法 |
| CN103272599A (zh) * | 2013-06-20 | 2013-09-04 | 南京信息工程大学 | 一种3d花状氧化铜纳米光催化剂的制备方法 |
| CN103623823A (zh) * | 2013-12-06 | 2014-03-12 | 河北工业大学 | 一种碳球@CuO核-壳型复合微球及其制备方法和应用 |
| CN106238050A (zh) * | 2015-06-12 | 2016-12-21 | 中国科学院苏州纳米技术与纳米仿生研究所 | 氧化铜/氧化亚铜复合光催化材料及其制备方法 |
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- 2017-03-30 CN CN201710201077.9A patent/CN107051459A/zh active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070181A (zh) * | 2011-01-14 | 2011-05-25 | 浙江大学 | 一种氧化亚铜的制备方法 |
| CN102357659A (zh) * | 2011-07-27 | 2012-02-22 | 西安交通大学 | 一种Cu-Cu2O异质结的制备方法 |
| CN103272599A (zh) * | 2013-06-20 | 2013-09-04 | 南京信息工程大学 | 一种3d花状氧化铜纳米光催化剂的制备方法 |
| CN103623823A (zh) * | 2013-12-06 | 2014-03-12 | 河北工业大学 | 一种碳球@CuO核-壳型复合微球及其制备方法和应用 |
| CN106238050A (zh) * | 2015-06-12 | 2016-12-21 | 中国科学院苏州纳米技术与纳米仿生研究所 | 氧化铜/氧化亚铜复合光催化材料及其制备方法 |
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