CN107486213A - 一种中空BiVO4微米片光催化剂的制备方法 - Google Patents
一种中空BiVO4微米片光催化剂的制备方法 Download PDFInfo
- Publication number
- CN107486213A CN107486213A CN201710770016.4A CN201710770016A CN107486213A CN 107486213 A CN107486213 A CN 107486213A CN 201710770016 A CN201710770016 A CN 201710770016A CN 107486213 A CN107486213 A CN 107486213A
- Authority
- CN
- China
- Prior art keywords
- bivo
- hollow
- micron film
- solution
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 40
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002105 nanoparticle Substances 0.000 claims abstract description 35
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 30
- 239000010941 cobalt Substances 0.000 claims abstract description 30
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229940063013 borate ion Drugs 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 230000015556 catabolic process Effects 0.000 claims abstract description 5
- 239000000356 contaminant Substances 0.000 claims abstract description 5
- 238000006731 degradation reaction Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 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 claims description 7
- 229940043267 rhodamine b Drugs 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 229910019501 NaVO3 Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229960001484 edetic acid Drugs 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 229910000428 cobalt oxide Inorganic materials 0.000 description 9
- 239000003426 co-catalyst Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种中空BiVO4微米片光催化剂的制备方法，包括：合成中空BiVO4微米片及硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片。本发明的有益效果在于：所需原料来源丰富、合成方法简单、可规模制备、重复性好，材料稳定性高；本发明制备的材料可用于光催化降解有机污染物、光催化分解水产氧，具有很好的实用价值和应用前景。
Description
技术领域
本发明涉及无机功能纳米材料技术领域，具体涉及一种硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片光催化剂的制备方法。
背景技术
环境污染和能源短缺已成为制约人类社会可持续发展的重要问题。开发新型能源与环境净化材料已经成为全人类的重大课题。太阳能是最理想的可再生资源，利用绿色的太阳光驱动降解有机污染物，这种光催化技术已成为解决环境问题的重要手段。
光催化技术的核心是新型高效光催化剂的开发。商品化的P25光催化剂已被广泛应用。但是该产品存在光谱响应范围太窄之不足，只能利用太阳光谱中的紫外线部分，这大大限制了该产品的应用范围。开发新型高效的可见光响应的催化剂是当前研究的热点，也代表光催化产品开发的新方向。
BiVO4是一种可见光响应的光催化剂，已被广泛应用于光催化降解有机污染物、分解水、以及光电化学池。但是未经修饰的BiVO4的光催化活性仍不理想，难以满足实际的应用。通过合成纳米结构、贵金属修饰、掺杂、构筑异质结、助催化剂负载等手段能够有效提升BiVO4的光催化活性。但是目前的方法存在难以规模制备、操作繁杂、成本高等不足。利用地球含量丰富、价格低廉的原材料做掺杂剂和助催化剂，通过掺杂和助催化剂的共修饰，则可以进一步提升BiVO4的光催化活性。
发明内容
针对现有技术的不足，本发明旨在提供一种中空BiVO4微米片光催化剂的制备方法，实现制备硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片光催化剂。
为了实现上述目的，本发明采用如下技术方案：
一种中空BiVO4微米片光催化剂的制备方法，包括如下步骤：
S1合成中空BiVO4微米片：
1.1)将BiVO4·5H2O加入到稀硝酸溶液中，搅拌使其溶解，得到溶液A；
1.2)将NaVO3与乙二胺四乙酸加入到NaOH溶液中，搅拌使其溶解，得到溶液B；
1.3)将溶液B加入到溶液A中得到混合溶液并调节pH至4.6-5；然后加入到反应釜中，180℃反应24h，产物经水洗，烘干，即可得中空BiVO4微米片；
S2制备硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片：
2.1)将硝酸钴和硼酸钠，加入到乙醇与水的混合溶液中，搅拌使其溶解；
2.2)将步骤1.3)中制备得到的中空BiVO4微米片加入到步骤2.1)中得到的溶解有硝酸钴和硼酸钠的乙醇与水的混合溶液中，蒸干，在氩气气氛中200℃煅烧24h，即得硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片。
需要说明的是，步骤S1具体为：
1.1)将2mL的浓硝酸加入10mL的蒸馏水中稀释后，再加入5mmol的BiVO4·5H2O，搅拌使其溶解，得到溶液A；
1.2)将5mmol的NaVO3与1g的乙二胺四乙酸加入到8mL浓度为4mmol/L的NaOH溶液中，搅拌使其溶解，得到溶液B；
1.3)将溶液B加入到溶液A中，用4mmol/L NaOH溶液调节pH至4.6-5，然后加入到50mL的反应釜中，180℃反应24h，产物经水洗，烘干，即可得中空BiVO4微米片。
需要说明的是，所述步骤S2具体如下：
2.1)将10mg的硝酸钴和10mg的硼酸钠，溶解于20mL体积比为1:1的乙醇与水的混合溶液中；
2.2)将500mg步骤1.3)中制备得到的中空BiVO4微米片加入步骤2.1)的混合溶液中，蒸干，在氩气气氛中200℃煅烧24h，即可得硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片。
上述中空BiVO4微米片光催化剂的制备方法制备得到的硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片可应用于降解污染物中。
需要说明的是，硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片在光催化降解染料罗丹明B中作为光催化剂。
本发明的有益效果在于：
1、通过一锅水热合成路线得到中空BiVO4微米片，可实现规模化制备。
2、选择由高丰度、低成本的元素钴与硼作为助催化剂和掺杂剂，通过简单的浸渍法可同时实现硼酸根与氧化钴纳米颗粒对中空BiVO4微米片的共同修饰，减少了操作程序。
3、相比较中空BiVO4微米片、氧化钴纳米颗粒修饰的中空BiVO4微米片以及硼酸根掺杂的中空BiVO4微米片，本发明的硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片由于有效的载流子分离以及增强的表面催化活性而显示出最佳的光催化活性，可应用于环境净化领域。
4、本发明所需原料来源丰富、路线简单、重复性好、易于规模化生产。
附图说明
图1为中空BiVO4微米片的X-射线衍射花样。
图2中空BiVO4微米片的扫描电镜像。
图3为硼酸根离子掺杂与氧化钴纳米颗粒负载共修饰的中空BiVO4微米片的X-射线衍射花样。
图4为硼酸根离子掺杂与氧化钴纳米颗粒负载共修饰的中空BiVO4微米片的扫描电镜像。
图5为硼酸根离子掺杂与氧化钴纳米颗粒负载共修饰的中空BiVO4微米片的透射电镜像。
图6为硼酸根离子掺杂与氧化钴纳米颗粒负载共修饰的中空BiVO4微米片的元素分布。
图7为中空BiVO4微米片以及硼酸根离子掺杂与氧化钴纳米颗粒负载共修饰的中空BiVO4微米片的紫外漫反射谱图。
图8为中空BiVO4微米片以及硼酸根离子掺杂与氧化钴纳米颗粒负载共修饰的中空BiVO4微米片的荧光光谱图。
图9为中空BiVO4微米片以及硼酸根离子掺杂与氧化钴纳米颗粒负载共修饰的中空BiVO4微米片的光催化活性比较实验结果示意图。
具体实施方式
以下将结合附图对本发明作进一步的描述，需要说明的是，本实施例以本技术方案为前提，给出了详细的实施方式和具体的操作过程，但本发明的保护范围并不限于本实施例。
一种硼酸根离子掺杂与氧化钴纳米颗粒负载共修饰的中空BiVO4微米片光催化剂的制备方法，包括以下步骤：
S1合成中空BiVO4微米片：
1.1)将2mL的浓硝酸加入10mL的蒸馏水中稀释后，再加入5mmol的BiVO4·5H2O，搅拌使其溶解，得到溶液A；
1.2)将5mmol的NaVO3与1g的乙二胺四乙酸加入到8mL浓度为4mmol/L的NaOH溶液中，搅拌使其溶解，得到溶液B；
1.3)将溶液B加入到溶液A中，用4mmol/LNaOH调节溶液的最终pH为4.6-5；将此溶液加入到50mL的反应釜中，180℃反应24h，产物经水洗，烘干，即可得中空BiVO4微米片；
S2制备硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片：
2.1)将10mg的硝酸钴和10mg的硼酸钠，溶解于20mL体积比为1:1的乙醇与水的混合溶液中。
2.2将500mg步骤1.3)中制备的中空BiVO4微米片加入该混合溶液，蒸干，在氩气气氛中200℃煅烧24h，即可得硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片。
上述制备方法制备得到的硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片在光催化降解有机污染物中的应用，具体在光催化降解水体中染料罗丹明B方面的应用。
步骤S1中所获得中空BiVO4微米片的X-射线衍射花样如图1所示。所有的衍射峰可以指标化为纯相的BiVO4。扫描电镜观察表明，产物为中空的微米片结构(图2)。
步骤S2所获得的硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片的X-射线衍射花样如图3所示。所有的衍射峰可以指标化为纯相的BiVO4，没有其它杂质相被探测到，表明产物中氧化钴的成分较少，硼酸根的掺杂不会影响BiVO4的相结构。产物的扫描电镜像(图4)显示，经过硼酸根掺杂与氧化钴负载，产物的形貌没有明显的变化。从透射电镜像能够看出，氧化钴纳米颗粒被均匀的负载在BiVO4表面(图5)。元素分布图也证实产物中含有Bi、V、Co、O、B元素，硼酸根与氧化钴纳米颗粒均匀的分散在中空BiVO4微米片表面(图6)。
进一步地，步骤S1与S2中获得的中空BiVO4微米片与经过硼酸根掺杂与氧化钴纳米颗粒负载后的中空BiVO4微米片的紫外漫反射谱与荧光光谱分别如图7与图8所示。紫外漫反射谱分析表明，经硼酸根掺杂与氧化钴纳米颗粒修饰后的中空BiVO4微米片的光谱响应范围没有明显的变化。而荧光光谱测试显示经硼酸根掺杂与氧化钴纳米颗粒修饰后的中空BiVO4微米片的荧光性能下降，表明硼酸根掺杂与氧化钴纳米颗粒修饰促进了光生载流子的有效分离。
下面通过实验说明中空BiVO4微米片和硼酸根掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片的光催化性能：
光催化反应光源为500W氙灯(配有400nm的滤光片)，反应在室温下进行，每次催化实验催化剂的用量为0.1g，以罗丹明B(10-5mol/L，100mL)溶液作为降解对象，对光催化剂的性能进行评价。在光照前，催化剂放入染料溶液中在暗处搅拌8h，达到吸附脱附平衡后，打开光源，在磁力搅拌下进行光照，每隔固定的时间取样，进行离心后取上层清夜进行吸光度测试。实验结果如图9所示。由图9可知，经过硼酸根掺杂与氧化钴纳米颗粒修饰后的中空BiVO4微米片展现出了优秀的光催化活性。可见光照射下，修饰后的中空BiVO4微米片在3h内就可以将罗丹明B几乎完全降解。而可见光辐照下，在没有任何催化剂时，罗丹明B本身稳定且基本不降解。而未经修饰的中空BiVO4微米片，3h内，仅有42％的罗丹明B被降解。
对于本领域的技术人员来说，可以根据以上的技术方案和构思，作出各种相应的改变和变形，而所有的这些改变和变形都应该包括在本发明权利要求的保护范围之内。
Claims (5)
1.一种中空BiVO4微米片光催化剂的制备方法，其特征在于，包括如下步骤：
S1合成中空BiVO4微米片：
1.1)将BiVO4·5H2O加入到稀硝酸溶液中，搅拌使其溶解，得到溶液A；
1.2)将NaVO3与乙二胺四乙酸加入到NaOH溶液中，搅拌使其溶解，得到溶液B；
1.3)将溶液B加入到溶液A中得到混合溶液并调节pH至4.6-5；然后加入到反应釜中，180℃反应24h，产物经水洗，烘干，即可得中空BiVO4微米片；
S2制备硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片：
2.1)将硝酸钴和硼酸钠，加入到乙醇与水的混合溶液中，搅拌使其溶解；
2.2)将步骤1.3)中制备得到的中空BiVO4微米片加入到步骤2.1)中得到的溶解有硝酸钴和硼酸钠的乙醇与水的混合溶液中，蒸干，在氩气气氛中200℃煅烧24h，即得硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片。
2.根据权利要求1所述的中空BiVO4微米片光催化剂的制备方法，其特征在于，步骤S1具体为：
1.1)将2mL的浓硝酸加入10mL的蒸馏水中稀释后，再加入5mmol的BiVO4·5H2O，搅拌使其溶解，得到溶液A；
1.2)将5mmol的NaVO3与1g的乙二胺四乙酸加入到8mL浓度为4mmol/L的NaOH溶液中，搅拌使其溶解，得到溶液B；
1.3)将溶液B加入到溶液A中，用4mmol/L NaOH溶液调节pH至4.6-5，然后加入到50mL的反应釜中，180℃反应24h，产物经水洗，烘干，即可得中空BiVO4微米片。
3.根据权利要求1所述的中空BiVO4微米片光催化剂的制备方法，其特征在于，所述步骤S2具体如下：
2.1)将10mg的硝酸钴和10mg的硼酸钠，溶解于20mL体积比为1:1的乙醇与水的混合溶液中；
2.2)将500mg步骤1.3)中制备得到的中空BiVO4微米片加入步骤2.1)的混合溶液中，蒸干，在氩气气氛中200℃煅烧24h，即可得硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片。
4.权利要求1所述中空BiVO4微米片光催化剂的制备方法制备得到的硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片在降解污染物中的应用。
5.根据权利要求4所述的应用，其特征在于，硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片在光催化降解染料罗丹明B中作为光催化剂。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710377076X | 2017-05-25 | ||
| CN201710377076 | 2017-05-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107486213A true CN107486213A (zh) | 2017-12-19 |
| CN107486213B CN107486213B (zh) | 2020-01-31 |
Family
ID=60651156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710770016.4A Expired - Fee Related CN107486213B (zh) | 2017-05-25 | 2017-08-31 | 一种中空BiVO4微米片光催化剂的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107486213B (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109453759A (zh) * | 2019-01-02 | 2019-03-12 | 中南大学 | 铋量子点修饰的钒酸铋中空纳米结构的制备及其应用 |
| CN110180528A (zh) * | 2019-05-08 | 2019-08-30 | 陕西科技大学 | 一步溶剂热法制备La/B共掺杂BiVO4-OVs/rGO纳米复合材料及其应用 |
| CN110273145A (zh) * | 2019-07-03 | 2019-09-24 | 安徽师范大学 | 一种纳米花状的Bi-Co-O纳米材料及其制备方法和应用 |
| CN111146004A (zh) * | 2020-01-10 | 2020-05-12 | 北京化工大学 | 一种金属羟基氧化物复合B-BiVO4光电阳极及其制备方法 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5273577A (en) * | 1992-01-16 | 1993-12-28 | Basf Aktiengesellschaft | Bismuth phosphovanadate pigments |
| CN1683074A (zh) * | 2005-03-11 | 2005-10-19 | 南京大学 | 可见光响应型光催化薄膜层的制备方法 |
| CN102764659A (zh) * | 2011-05-06 | 2012-11-07 | 中国科学院合肥物质科学研究院 | 钴修饰的钨酸铋复合光催化剂及其制备方法和用途 |
| CN104138755A (zh) * | 2014-07-09 | 2014-11-12 | 盐城工学院 | 具有纳米空心结构的BiVO4光催化材料的制备方法 |
| CN106622231A (zh) * | 2016-12-30 | 2017-05-10 | 温州大学 | Pt/BiVO4片状结构复合光催化剂的合成及其应用 |
-
2017
- 2017-08-31 CN CN201710770016.4A patent/CN107486213B/zh not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5273577A (en) * | 1992-01-16 | 1993-12-28 | Basf Aktiengesellschaft | Bismuth phosphovanadate pigments |
| CN1683074A (zh) * | 2005-03-11 | 2005-10-19 | 南京大学 | 可见光响应型光催化薄膜层的制备方法 |
| CN102764659A (zh) * | 2011-05-06 | 2012-11-07 | 中国科学院合肥物质科学研究院 | 钴修饰的钨酸铋复合光催化剂及其制备方法和用途 |
| CN104138755A (zh) * | 2014-07-09 | 2014-11-12 | 盐城工学院 | 具有纳米空心结构的BiVO4光催化材料的制备方法 |
| CN106622231A (zh) * | 2016-12-30 | 2017-05-10 | 温州大学 | Pt/BiVO4片状结构复合光催化剂的合成及其应用 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109453759A (zh) * | 2019-01-02 | 2019-03-12 | 中南大学 | 铋量子点修饰的钒酸铋中空纳米结构的制备及其应用 |
| CN110180528A (zh) * | 2019-05-08 | 2019-08-30 | 陕西科技大学 | 一步溶剂热法制备La/B共掺杂BiVO4-OVs/rGO纳米复合材料及其应用 |
| CN110273145A (zh) * | 2019-07-03 | 2019-09-24 | 安徽师范大学 | 一种纳米花状的Bi-Co-O纳米材料及其制备方法和应用 |
| CN111146004A (zh) * | 2020-01-10 | 2020-05-12 | 北京化工大学 | 一种金属羟基氧化物复合B-BiVO4光电阳极及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107486213B (zh) | 2020-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Patil et al. | Recent advances in non-metals-doped TiO2 nanostructured photocatalysts for visible-light driven hydrogen production, CO2 reduction and air purification | |
| Wang et al. | Hydroxyl-regulated BiOI nanosheets with a highly positive valence band maximum for improved visible-light photocatalytic performance | |
| Meng et al. | Construction of g-C3N4/ZIF-67 photocatalyst with enhanced photocatalytic CO2 reduction activity | |
| CN110180548B (zh) | 一维氧化铟中空纳米管/二维铁酸锌纳米片异质结复合材料及其在去除水体污染物中的应用 | |
| Lian et al. | Pt-enhanced mesoporous Ti3+/TiO2 with rapid bulk to surface electron transfer for photocatalytic hydrogen evolution | |
| Cheng et al. | Copper-decorated TiO2 nanorod thin films in optofluidic planar reactors for efficient photocatalytic reduction of CO2 | |
| Koca et al. | Photocatalytic hydrogen production by direct sun light from sulfide/sulfite solution | |
| Feng et al. | Postillumination activity in a single-phase photocatalyst of Mo-doped TiO2 nanotube array from its photocatalytic “memory” | |
| CN107486213A (zh) | 一种中空BiVO4微米片光催化剂的制备方法 | |
| CN106076364B (zh) | 一种高效CdS-CdIn2S4超结构光催化剂的制备方法 | |
| Yang et al. | 2D WO3–x nanosheet with rich oxygen vacancies for efficient visible-light-driven photocatalytic nitrogen fixation | |
| Wang et al. | Preparation of CdS-P25/ZIF-67 composite material and its photocatalytic CO2 reduction performance | |
| CN106552651B (zh) | 一种Bi12O17Br2光催化剂的合成及应用方法 | |
| Sadeghzadeh-Attar | Enhanced photocatalytic hydrogen evolution by novel Nb-doped SnO2/V2O5 heteronanostructures under visible light with simultaneous basic red 46 dye degradation | |
| Baoum et al. | Development of CuCr 2 O 4 nanocomposite adopting decoration with polyaniline for acridine orange dye degradation | |
| CN107282077A (zh) | 一种光催化固氮催化剂的制备方法及其应用 | |
| CN109985618A (zh) | 一种H占据BiVO4-OVs的光催化材料、制备方法及其应用 | |
| CN108993550A (zh) | 一种表面氧空位改性的溴氧铋光催化剂及其制备方法 | |
| CN108686665A (zh) | 一种纳米棒铁酸锌原位复合片层二氧化钛光催化材料的制备方法 | |
| CN111558375A (zh) | 一种高活性的单原子铁修饰TiO2空心微球的制备方法及其在光催化氧化NO中的应用 | |
| CN106044842A (zh) | 一种扇形羟基氟化锌的制备方法及其应用 | |
| Rawool et al. | Lab scale optimization of various factors for photocatalytic hydrogen generation over low cost Cu0. 02Ti0. 98O2-δ photocatalyst under UV/Visible irradiation and sunlight | |
| CN107417503A (zh) | 一种利用太阳光氧化芳香醇制取芳香醛的方法 | |
| CN107537520A (zh) | 一种溴氧化铋‑氧化铜纳米复合光催化剂及其制备方法 | |
| Liu et al. | A comparison of N‐doped TiO2 photocatalysts preparation methods and studies on their catalytic activity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200131 Termination date: 20210831 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |