CN105688968A - 一种钒酸铋/氮化硼复合光催化材料及其制备方法 - Google Patents
一种钒酸铋/氮化硼复合光催化材料及其制备方法 Download PDFInfo
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 71
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 39
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 39
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002135 nanosheet Substances 0.000 claims abstract description 42
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims abstract description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 13
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000000725 suspension Substances 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 20
- 239000012286 potassium permanganate Substances 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 239000004317 sodium nitrate Substances 0.000 claims description 10
- 235000010344 sodium nitrate Nutrition 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- YAWXJZPVVKDSMZ-UHFFFAOYSA-N [Bi].[V].[Bi] Chemical compound [Bi].[V].[Bi] YAWXJZPVVKDSMZ-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000002055 nanoplate Substances 0.000 claims 1
- GTTYPHLDORACJW-UHFFFAOYSA-N nitric acid;sodium Chemical compound [Na].O[N+]([O-])=O GTTYPHLDORACJW-UHFFFAOYSA-N 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 238000001816 cooling Methods 0.000 abstract description 8
- 230000005012 migration Effects 0.000 abstract description 8
- 238000013508 migration Methods 0.000 abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000969 carrier Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000005284 excitation Effects 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 8
- 238000010335 hydrothermal treatment Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
本发明公开了一种钒酸铋/氮化硼复合光催化材料,以氮化硼纳米片为催化剂载体,将钒酸铋负载于氮化硼纳米片上,其中氮化硼纳米片和钒酸铋的摩尔比为1:0.01~0.6。本发明还公开了其制备方法,将五水硝酸铋溶解于硝酸溶液,然后加入氮化硼纳米片和偏钒酸钠得到混合溶液,将混合溶液超声后转移至水热反应釜,将水热反应釜置于烘箱中进行水热反应,待自然冷却至室温,将产物离心分离洗涤,干燥即得。本发明复合光催化材料,利用氮化硼纳米片表面存在的氮空位导致其具有一定的电负性,将光照激发后钒酸铋价带的光生空穴吸引以促进空穴的迁移,进而提高光生载流子的迁移效率;氮化硼纳米片大的比表面积有利于增加复合体系的吸附性能。
Description
技术领域
本发明属于无机环保催化材料技术领域,具体涉及一种钒酸铋/氮化硼复合光催化材料,本发明还涉及该复合光催化材料的制备方法。
背景技术
半导体光催化技术以其高效的特点日益受到人们的重视,用于解决环境污染问题和太阳能转换。对于高效光催化剂的选择是半导体光催化技术最重要的一个方面,目前,大约有200多种半导体可用于光催化反应,但是,较低的量子效率和严重的光腐蚀现象影响了大多数光催化剂的应用。因此,如何提高半导体光催化剂光生电子空穴的分离效率以抑制其快速复合是光催化技术所面临的问题。通常情况,催化剂的晶体结构、颗粒尺寸、形貌、特定暴露晶面和表面修饰(如,贵金属表面沉积、碳纳米管修饰、石墨烯修饰以及半导体复合等)是提高光生电子空穴分离效率的重要途径,但是,这些方法都是以提高光生电子的传输速率为基础的,然而,通过提高光生空穴的迁移速率以提高光生载流子的分离效率却被忽视。目前,改变光生空穴的迁移速率有两种方法,第一,设计具有能带结构比配的半导体复合体系,在体系吸收光子能量被激发后,可以实现空穴从一种半导体的价带迁移至另一种半导体的价带,但是这种形式的迁移会减弱空穴的氧化能力。另一种方法是在半导体光催化剂表面修饰空穴捕获剂(如RuO2、NiO、IrO2等),这种方法在光解水制氢的反应中是有效的,但是在光催化降解有机物的反应中是否有效还未见报道,因此,这类方法的应用具有一定的局限性。开发一种新型有效的能够促进光生空穴迁移速率的方法是提高半导体光催化剂光生载流子分离效率的另一个重要途径。
发明内容
本发明的目的是提供一种钒酸铋/氮化硼复合光催化材料,解决了现有都是以提高光生电子的传输速率为基础的,然而通过提高光生空穴的迁移速率以提高光生载流子的分离效率却被忽视的问题。
本发明的另一个目的是提供一种钒酸铋/氮化硼复合光催化材料的制备方法。
本发明所采用的技术方案是,一种钒酸铋/氮化硼复合光催化材料,以氮化硼纳米片为催化剂载体,将钒酸铋负载于氮化硼纳米片上,其中氮化硼纳米片和钒酸铋的摩尔比为1:0.01~0.6。
本发明所采用的另一个技术方案是,一种钒酸铋/氮化硼复合光催化材料的制备方法,将五水硝酸铋溶解于浓度为10%的硝酸溶液,然后加入氮化硼纳米片和偏钒酸钠得到混合溶液,将混合溶液超声搅拌均匀后转移至水热反应釜,将水热反应釜置于烘箱中进行水热反应,待自然冷却至室温,将得到的产物离心分离洗涤,干燥,得到钒酸铋/氮化硼复合光催化材料。
本发明的特点还在于,
五水硝酸铋和硝酸的质量比为1:40~100。
氮化硼纳米片和五水硝酸铋的摩尔比为1:0.01~0.6。
五水硝酸铋和偏钒酸钠的摩尔比为1:1。
水热反应温度为160~220℃,时间为5~30h。
氮化硼纳米片的具体制备方法为:将六方氮化硼粉体、硝酸钠和浓硫酸混合后置于冰水浴中搅拌均匀得到悬浮液,将高锰酸钾缓慢加入到悬浮液中,持续搅拌反应8~24h后加入双氧水持续搅拌反应0.5~1h,待反应结束后将悬浮液在3000rpm条件下离心10min,将上层悬浮液用微孔抽滤,去离子水洗涤至中性,干燥后得到氮化硼纳米片。
六方氮化硼粉体、硝酸钠和浓硫酸质量比为1:0.5~1:30~60。
六方氮化硼粉体和高锰酸钾的质量比为1:0.5~1。
高锰酸钾和双氧水的质量比为1:8~16。
本发明的有益效果是,本发明钒酸铋/氮化硼复合光催化材料,利用氮化硼纳米片表面存在的氮空位导致其具有一定的电负性,将光照激发后钒酸铋价带的光生空穴吸引以促进空穴的迁移,进而提高光生载流子的迁移效率;此外,氮化硼纳米片大的比表面积有利于增加复合体系的吸附性能,这些对于光催化效率的提高都是有利的。
本发明钒酸铋/氮化硼复合光催化材料的制备方法,过程简单,反应条件温和,合成效率高,成本低。
具体实施方式
下面结合具体实施方式对本发明进行详细说明。
本发明一种钒酸铋/氮化硼复合光催化材料,以氮化硼纳米片为催化剂载体,将钒酸铋负载于氮化硼纳米片上,其中氮化硼纳米片和钒酸铋的摩尔比为1:0.01~0.6。
氮化硼具有与石墨相似的结构,但是与石墨相比,氮化硼还具有很多优异的物理化学特性,如耐高温、高导热、优异的电学性能、良好的高温稳定性以及化学稳定性等。层状氮化硼纳米片表面由于存在氮空位会导致其具有一定的电负性,如果以氮化硼纳米片作为光催化剂载体,将半导体光催化剂负载于氮化硼纳米片上,体系受光照激发后,氮化硼纳米片表面的电负性会吸引半导体价带的光生空穴以促进空穴的迁移,进而提高光生载流子的迁移效率。此外,氮化硼纳米片大的比表面有利于增加复合体系的吸附性能,这些对于光催化效率都是有利的。
上述钒酸铋/氮化硼复合光催化材料的制备方法,具体按照以下步骤实施:
步骤1,将六方氮化硼粉体、硝酸钠和浓硫酸按质量比为1:0.5~1:30~60混合后置于冰水浴中搅拌均匀得到悬浮液,将高锰酸钾缓慢加入到悬浮液中,其中六方氮化硼粉体和高锰酸钾的质量比为1:0.5~1,持续搅拌反应8~24h后加入双氧水持续搅拌反应0.5~1h,其中高锰酸钾和双氧水的质量比为1:8~16,待反应结束后将悬浮液在3000rpm条件下离心10min,将上层悬浮液用微孔抽滤,去离子水洗涤至中性,干燥后得到氮化硼纳米片;
步骤2,将五水硝酸铋溶解于浓度为10%的硝酸溶液,五水硝酸铋和硝酸的质量比为1:40~100,然后加入氮化硼纳米片和偏钒酸钠得到混合溶液,其中氮化硼纳米片和五水硝酸铋的摩尔比为1:0.01~0.6,五水硝酸铋和偏钒酸钠的摩尔比为1:1,将混合溶液超声搅拌均匀后转移至水热反应釜,将水热反应釜置于烘箱中加热至160~220℃水热处理5~30h,待自然冷却至室温,将得到的产物离心分离洗涤,干燥,得到钒酸铋/氮化硼复合光催化材料。
实施例1
步骤1,将1g六方氮化硼粉体、0.5g硝酸钠和30g浓硫酸混合后置于冰水浴中搅拌均匀得到悬浮液,将0.5g高锰酸钾缓慢加入到悬浮液中,持续搅拌反应8h后加入4g双氧水持续搅拌反应0.5h,待反应结束后将悬浮液在3000rpm条件下离心10min,将上层悬浮液用微孔抽滤,去离子水洗涤至中性,60℃干燥12h,得到氮化硼纳米片;
步骤2,将0.49g五水硝酸铋溶解于19.6g浓度为10%的硝酸溶液,然后加入2.48g氮化硼纳米片和0.12g偏钒酸钠得到混合溶液,将混合溶液超声搅拌均匀后转移至水热反应釜,将水热反应釜置于烘箱中加热至160℃水热处理5h,待自然冷却至室温,将得到的产物离心分离洗涤,于80℃干燥12h,得到钒酸铋/氮化硼复合光催化材料。
实施例2
步骤1,将1g六方氮化硼粉体、1g硝酸钠和60g浓硫酸混合后置于冰水浴中搅拌均匀得到悬浮液,将1g高锰酸钾缓慢加入到悬浮液中,持续搅拌反应24h后加入16g双氧水持续搅拌反应1h,待反应结束后将悬浮液在3000rpm条件下离心10min,将上层悬浮液用微孔抽滤,去离子水洗涤至中性,60℃干燥12h,得到氮化硼纳米片;
步骤2,将29.1g五水硝酸铋溶解于2910g浓度为10%的硝酸溶液,然后加入2.48g氮化硼纳米片和7.32g偏钒酸钠得到混合溶液,将混合溶液超声搅拌均匀后转移至水热反应釜,将水热反应釜置于烘箱中加热至220℃水热处理30h,待自然冷却至室温,将得到的产物离心分离洗涤,于80℃干燥12h,得到钒酸铋/氮化硼复合光催化材料。
实施例3
步骤1,将1g六方氮化硼粉体、0.5g硝酸钠和30g浓硫酸混合后置于冰水浴中搅拌均匀得到悬浮液,将0.5g高锰酸钾缓慢加入到悬浮液中,持续搅拌反应8h后加入4g双氧水持续搅拌反应0.5h,待反应结束后将悬浮液在3000rpm条件下离心10min,将上层悬浮液用微孔抽滤,去离子水洗涤至中性,60℃干燥12h,得到氮化硼纳米片;
步骤2,将29.1g五水硝酸铋溶解于2910g浓度为10%的硝酸溶液,然后加入2.48g氮化硼纳米片和7.32g偏钒酸钠得到混合溶液,将混合溶液超声搅拌均匀后转移至水热反应釜,将水热反应釜置于烘箱中加热至220℃水热处理30h,待自然冷却至室温,将得到的产物离心分离洗涤,于80℃干燥12h,得到钒酸铋/氮化硼复合光催化材料。
实施例4
步骤1,将1g六方氮化硼粉体、1g硝酸钠和60g浓硫酸混合后置于冰水浴中搅拌均匀得到悬浮液,将1g高锰酸钾缓慢加入到悬浮液中,持续搅拌反应24h后加入16g双氧水持续搅拌反应1h,待反应结束后将悬浮液在3000rpm条件下离心10min,将上层悬浮液用微孔抽滤,去离子水洗涤至中性,60℃干燥12h,得到氮化硼纳米片;
步骤2,将0.49g五水硝酸铋溶解于19.6g浓度为10%的硝酸溶液,然后加入2.48g氮化硼纳米片和0.12g偏钒酸钠得到混合溶液,将混合溶液超声搅拌均匀后转移至水热反应釜,将水热反应釜置于烘箱中加热至160℃水热处理5h,待自然冷却至室温,将得到的产物离心分离洗涤,于80℃干燥12h,得到钒酸铋/氮化硼复合光催化材料。
实施例5
步骤1,将1g六方氮化硼粉体、0.8g硝酸钠和40g浓硫酸混合后置于冰水浴中搅拌均匀得到悬浮液,将0.8g高锰酸钾缓慢加入到悬浮液中,持续搅拌反应12h后加入8g双氧水持续搅拌反应0.8h,待反应结束后将悬浮液在3000rpm条件下离心10min,将上层悬浮液用微孔抽滤,去离子水洗涤至中性,60℃干燥12h,得到氮化硼纳米片;
步骤2,将0.49g五水硝酸铋溶解于29.4g浓度为10%的硝酸溶液,然后加入0.062g氮化硼纳米片和0.12g偏钒酸钠得到混合溶液,将混合溶液超声搅拌均匀后转移至水热反应釜,将水热反应釜置于烘箱中加热至180℃水热处理10h,待自然冷却至室温,将得到的产物离心分离洗涤,于80℃干燥12h,得到钒酸铋/氮化硼复合光催化材料。
实施例6
步骤1,将1g六方氮化硼粉体、0.6g硝酸钠和50g浓硫酸混合后置于冰水浴中搅拌均匀得到悬浮液,将0.9g高锰酸钾缓慢加入到悬浮液中,持续搅拌反应20h后加入10.8g双氧水持续搅拌反应0.6h,待反应结束后将悬浮液在3000rpm条件下离心10min,将上层悬浮液用微孔抽滤,去离子水洗涤至中性,60℃干燥12h,得到氮化硼纳米片;
步骤2,将29.1g五水硝酸铋溶解于2328g浓度为10%的硝酸溶液,然后加入14.89g氮化硼纳米片和7.32g偏钒酸钠得到混合溶液,将混合溶液超声搅拌均匀后转移至水热反应釜,将水热反应釜置于烘箱中加热至200℃水热处理20h,待自然冷却至室温,将得到的产物离心分离洗涤,于80℃干燥12h,得到钒酸铋/氮化硼复合光催化材料。
Claims (10)
1.一种钒酸铋/氮化硼复合光催化材料,其特征在于,以氮化硼纳米片为催化剂载体,将钒酸铋负载于氮化硼纳米片上,其中氮化硼纳米片和钒酸铋的摩尔比为1:0.01~0.6。
2.一种钒酸铋/氮化硼复合光催化材料的制备方法,其特征在于,将五水硝酸铋溶解于浓度为10%的硝酸溶液,然后加入氮化硼纳米片和偏钒酸钠得到混合溶液,将混合溶液超声搅拌均匀后转移至水热反应釜,将水热反应釜置于烘箱中进行水热反应,待自然冷却至室温,将得到的产物离心分离洗涤,干燥,得到钒酸铋/氮化硼复合光催化材料。
3.根据权利要求2所述的钒酸铋/氮化硼复合光催化材料的制备方法,其特征在于,五水硝酸铋和硝酸的质量比为1:40~100。
4.根据权利要求2所述的钒酸铋/氮化硼复合光催化材料的制备方法,其特征在于,氮化硼纳米片和五水硝酸铋的摩尔比为1:0.01~0.6。
5.根据权利要求2所述的钒酸铋/氮化硼复合光催化材料的制备方法,其特征在于,五水硝酸铋和偏钒酸钠的摩尔比为1:1。
6.根据权利要求2所述的钒酸铋/氮化硼复合光催化材料的制备方法,其特征在于,水热反应温度为160~220℃,时间为5~30h。
7.根据权利要求2或4所述的钒酸铋/氮化硼复合光催化材料的制备方法,其特征在于,氮化硼纳米片的具体制备方法为:将六方氮化硼粉体、硝酸钠和浓硫酸混合后置于冰水浴中搅拌均匀得到悬浮液,将高锰酸钾缓慢加入到悬浮液中,持续搅拌反应8~24h后加入双氧水持续搅拌反应0.5~1h,待反应结束后将悬浮液在3000rpm条件下离心10min,将上层悬浮液用微孔抽滤,去离子水洗涤至中性,干燥后得到氮化硼纳米片。
8.根据权利要求7所述的钒酸铋/氮化硼复合光催化材料的制备方法,其特征在于,六方氮化硼粉体、硝酸钠和浓硫酸质量比为1:0.5~1:30~60。
9.根据权利要求7所述的钒酸铋/氮化硼复合光催化材料的制备方法,其特征在于,六方氮化硼粉体和高锰酸钾的质量比为1:0.5~1。
10.根据权利要求7所述的钒酸铋/氮化硼复合光催化材料的制备方法,其特征在于,高锰酸钾和双氧水的质量比为1:8~16。
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