CN105688955B - 一种改进的P掺杂TiO2光催化剂制备方法 - Google Patents
一种改进的P掺杂TiO2光催化剂制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000001228 spectrum Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
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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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Abstract
一种改进的P掺杂TiO2光催化剂的制备方法,以钛酸丁酯为前驱物,以气态磷化氢为P源,通过气‑液水热法、过滤、洗涤、干燥程序制备P掺杂TiO2光催化剂。本发明的优点是:该方法操作方便,工艺简单,所得催化剂中P多以间隙P形式存在,有利于提高光生电子‑空穴的分离和在可见光区的催化活性。
Description
技术领域
本发明涉及一种改进的P掺杂TiO2光催化剂制备方法。
背景技术
TiO2因其具有光催化效率高、价格便宜、化学稳定性好、无生物毒性等优点,近年来被广泛应用于环境污染治理和可再生能源领域。研究发现,P掺杂不仅能抑制锐钛矿型TiO2向金红石相转化,更可拓宽其光响应范围至可见光区,提高对太阳能的利用率。P掺杂提高TiO2在可见光下光催化活性的原因是,P以间隙式原子存在,即以P3+存在,形成一条掺杂能级位于TiO2禁带之内,成为光生电子-空穴对的分离中心,延长光生载流子的寿命,在可见光区具有更强的吸收能力。目前报道多以磷酸氢二钠、磷酸钠、磷酸等无机磷盐为P源,通过水热技术进行P的掺杂,所得到的P掺杂形式多为P替代Ti(即P5+),对可见光下光催化活性提高不明显。为更有效利用太阳能,通过改进的P掺杂方法,制备间隙P含量更多的P掺杂TiO2具有巨大的实际研究意义。
发明内容
本发明的目的是提供一种改进的P掺杂TiO2光催化剂制备方法,该方法操作方便,工艺简单,所得催化剂中P多以间隙P形式存在,有利于提高光生电子-空穴的分离和在可见光区的催化活性。
本发明的技术方案:
一种改进的P掺杂TiO2光催化剂制备方法,以钛酸丁酯为前驱物,以气态磷化氢为P源,通过水热法、过滤、洗涤、干燥程序制备P掺杂TiO2光催化剂,具体包括如下步骤:
1)将5-30ml钛酸丁酯溶于80ml无水乙醇中,剧烈搅拌,再缓慢滴加20ml去离子水,搅拌6h,然后放入带有聚四氟乙烯内衬和压力表的不锈钢高压水热反应釜中。
2)将一定体积比的磷化氢/氮气混合气体通入反应釜内的混合溶液中,保持一定压力并在180℃下保温12h。
3)将反应釜水冷至室温,产物经过滤、乙醇和去离子水洗涤,在室温下干燥24h,然后 80℃真空干燥12h,制得P掺杂TiO2光催化剂,通过X射线光电子能谱(XPS)分析结果显示,P元素中P3+含量为20-70%。
所述磷化氢与氮气的体积比为0.001-0.01∶1。
所述反应釜压力为0.1-0.5MPa。
本发明的优点是:工艺简单,耗能低,所得P掺杂TiO2光催化剂中P多以间隙P存在,有效提高其光生电子-空穴的分离和在可见光区的催化活性,有利于提高对太阳能的利用率。
具体实施方式
下面结合实施例对本发明进一步说明,但是它们并不是对本发明作任何限制。这里仅指出,本发明中使用的试剂和测试设备除特别标明出处之外,均为市售的通用产品。
实施例1:
一种改进的P掺杂TiO2光催化剂制备方法,包括如下步骤:
1)将10ml钛酸丁酯溶于80ml无水乙醇中,剧烈搅拌,再缓慢滴加20ml去离子水,搅拌6h,然后放入带有聚四氟乙烯内衬和压力表的不锈钢高压水热反应釜中。
2)将体积比为0.005∶1的磷化氢/氮气混合气体通入反应釜内的混合溶液中,在0.2MPa 压力和180℃下保温12h。
3)将反应釜水冷至室温,产物经过滤、乙醇和去离子水洗涤,在室温下干燥24h,然后 80℃真空干燥12h,制得P掺杂TiO2光催化剂,通过X射线光电子能谱(XPS)分析结果显示,P元素中P3+含量为45.5%。
实施例2:
一种改进的P掺杂TiO2光催化剂制备方法,包括如下步骤:
1)将23ml钛酸丁酯溶于80ml无水乙醇中,剧烈搅拌,再缓慢滴加20ml去离子水,搅拌6h,然后放入带有聚四氟乙烯内衬和压力表的不锈钢高压水热反应釜中。
2)将体积比为0.005∶1的磷化氢/氮气混合气体通入反应釜内的混合溶液中,在0.3MPa 压力和180℃下保温12h。
3)将反应釜水冷至室温,产物经过滤、乙醇和去离子水洗涤,在室温下干燥24h,然后 80℃真空干燥12h,制得P掺杂TiO2光催化剂,通过X射线光电子能谱(XPS)分析结果显示,P元素中P3+含量为58.7%。
实施例3:
一种改进的P掺杂TiO2光催化剂制备方法,包括如下步骤:
1)将23ml钛酸丁酯溶于80ml无水乙醇中,剧烈搅拌,再缓慢滴加20ml去离子水,搅拌6h,然后放入带有聚四氟乙烯内衬和压力表的不锈钢高压水热反应釜中。
2)将体积比为0.009∶1的磷化氢/氮气混合气体通入反应釜内的混合溶液中,在0.4MPa 压力和180℃下保温12h。
3)将反应釜水冷至室温,产物经过滤、乙醇和去离子水洗涤,在室温下干燥24h,然后 80℃真空干燥12h,制得P掺杂TiO2光催化剂,通过X射线光电子能谱(XPS)分析结果显示,P元素中P3+含量为69.3%。
本发明公开一种改进的P掺杂TiO2光催化剂制备方法,本领域技术人员可通过借鉴本文内容,适当改变工艺路线等环节实现,尽管本发明的方法已通过较佳实施例子进行了描述,相关技术人员明显能在不脱离本发明内容与范围内对本文所述的方法进行改动或重新组合,来实现最终结果。特别需要指出的是,所有相类似的替换和改动对本领域技术人员来说是显而易见的,它们都被视为包括在本发明的内容和范围。
Claims (3)
1.一种改进的P掺杂TiO2光催化剂制备方法,其特征在于:以钛酸丁酯为前驱物,以气态磷化氢为P源,通过水热法、过滤、洗涤、干燥程序制备P掺杂TiO2光催化剂,具体包括如下步骤:
1)将5-30ml钛酸丁酯溶于80ml无水乙醇中,剧烈搅拌,再缓慢滴加20ml去离子水,搅拌6h,然后放入带有聚四氟乙烯内衬和压力表的不锈钢高压水热反应釜中;
2)将一定体积比的磷化氢/氮气混合气体通入反应釜内的混合溶液中,保持一定压力并在180℃下保温12h;
3)将反应釜水冷至室温,产物经过滤、乙醇和去离子水洗涤,在室温下干燥24h,然后80℃真空干燥12h,制得P掺杂TiO2光催化剂,通过X射线光电子能谱(XPS)分析结果显示,P元素中P3+含量为20-70%。
2.根据权利要求1所述一种改进的P掺杂TiO2光催化剂制备方法,其特征在于:所述磷化氢与氮气的体积比为0.001-0.01∶1。
3.根据权利要求1所述一种改进的P掺杂TiO2光催化剂制备方法,其特征在于:所述反应釜压力为0.1-0.5MPa。
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CN103495429A (zh) * | 2013-07-19 | 2014-01-08 | 西安理工大学 | 一种磷掺杂二氧化钛粉体光催化剂的微波水热合成方法 |
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CN103495429A (zh) * | 2013-07-19 | 2014-01-08 | 西安理工大学 | 一种磷掺杂二氧化钛粉体光催化剂的微波水热合成方法 |
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