CN113522258B - 一种高效光催化氧化VOCs的催化剂的制备方法 - Google Patents
一种高效光催化氧化VOCs的催化剂的制备方法 Download PDFInfo
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- CN113522258B CN113522258B CN202010316508.8A CN202010316508A CN113522258B CN 113522258 B CN113522258 B CN 113522258B CN 202010316508 A CN202010316508 A CN 202010316508A CN 113522258 B CN113522258 B CN 113522258B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 title abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 45
- 239000002071 nanotube Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 230000001699 photocatalysis Effects 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 44
- 239000000843 powder Substances 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 239000010931 gold Substances 0.000 claims description 14
- 229910000510 noble metal Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 239000011858 nanopowder Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 238000005234 chemical deposition Methods 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 238000007084 catalytic combustion reaction Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 229910002710 Au-Pd Inorganic materials 0.000 description 12
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 12
- -1 polytetrafluoroethylene Polymers 0.000 description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940055221 silvera Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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Abstract
本发明公开了一种高效光催化氧化VOCs的催化剂的制备方法，利用还原态二氧化钛纳米管内腔的微纳空间，将催化活性组元高度分散在还原态二氧化钛纳米管内腔的孔道中，抑制催化剂的团聚和烧结，同时通过表面修饰或改性来进一步调节纳米管内活性组元的氧化性来提高催化性能和稳定性，有利于在光照射条件下高效光催化氧化VOCs转化为二氧化碳和水，起燃温度降低，催化燃烧速度加快，大大缩短了处理时间，降低了能耗，提高了效率。
Description
技术领域：
本发明涉及光催化技术领域，具体涉及一种高效光催化氧化VOCs的催化剂的制备方法。
背景技术：
挥发性有机物(VOCs)由于其扩散性强、毒性大、来源广泛等特点，严重威胁着人类生命安全和动植物赖以生存的自然环境。目前VOCs的处理方法主要有吸附回收、膜分离回收、冷凝回收、光/热催化氧化处理、热焚烧处理、生物降解以及低温等离子体氧化处理。光催化氧化和催化燃烧氧化技术是目前最具发展前景的处理技术之一。但热催化处理温度较高，能耗较大，而光催化温和但效率较低。因此开发中低温(150℃～300℃)光热协同催化氧化VOCs技术是今后的发展方向。实现中低温高效持续催化氧化VOCs的关键在于高效稳定催化剂的研发。目前催化氧化反应所使用的催化剂活性组元主要为贵金属(Au、Pd、Ru、Pt、Ag)以及金属氧化物(MnOx，In2O3、CeO2，WO2，V2O5，Cr2O3，Fe2O3，Co3O4，NiO，CuO，La2O3和ZrO2)。其中，过渡态金属氧化物基催化剂具有价格低廉并且性能稳定等优点，但是其催化效率偏低且难以提升；贵金属基催化剂虽然比较高效，但是其价格相对较高，未加以改性的贵金属基催化剂在反应过程中容易发生中毒且在高温下易发生颗粒团聚，导致失活。
发明内容：
本发明的目的是提供一种高效光催化氧化VOCs的催化剂的制备方法，利用空间限域效应以及电子调变理论，将催化氧化活性组元内嵌于还原态的二氧化钛纳米管内腔的孔道中，并通过二氧化钛纳米管表面修饰或改性来进一步调节管内活性组元的氧化性，解决了现有技术存在的问题。
本发明是通过以下技术方案予以实现的：
一种高效光催化氧化VOCs的催化剂的制备方法，该方法包括以下步骤：
1)水热法制备二氧化钛纳米管：将二氧化钛纳米粉加入到9-15moL/L的氢氧化钠溶液中，100～180℃搅拌下进行水热反应24～48h，自然冷却到室温，过滤、去离子水洗涤至洗液PH为7，将0.1～0.5moL/L的盐酸溶液加入到上述粉体中，搅拌5～10h，再次用去离子水洗涤至洗液PH为7，过滤，最后将所得粉体在60～100℃条件下干燥24-36h，然后在马弗炉中焙烧，升温速率为0.5～1℃/min，升温至200～400℃，保温1～10h，得到二氧化钛纳米管，记为TiO2NTs；
2)还原二氧化钛纳米管：二氧化钛纳米管用0.5～2M硼氢化钠水溶液还原反应5～720min，将反应后的产物抽滤后并用去离子水和乙醇清洗多次，最后放置于60～100℃烘箱中干燥10～20h得到还原态二氧化钛纳米管；或，二氧化钛纳米管放置于焙烧坩埚中，随后将其放置于气氛炉中，在氢气气氛下焙烧，反应温度为200～300℃，反应时间为60～720min，反应后冷却到室温得到还原态二氧化钛纳米管，记为H-TiO2NTs；
3)真空辅助超声等体积浸渍法将活性组元贵金属内嵌于还原态的二氧化钛纳米管：称取300～800mg还原后二氧化钛纳米，将2～10mL0.005g/mL贵金属乙醇溶液分多次滴加，每次滴加至粉体刚好浸湿为止，并将其放置于超声中用真空泵在负压下抽干，然后转移至坩埚中，并于管式炉在含有8％氢气和92％氩气的混合气氛中200～300℃退火1～10h得到催化氧化活性组元贵金属内嵌于还原的二氧化钛纳米管的产物，记为M@H-TiO2NTs，其中M为贵金属，为活性组元，贵金属包括铂、钯、金、钌、银中的一种或多种；
4)化学沉积法在表面负载金属氧化物催化助剂进行表面修饰：称取300～800mg步骤3)得到的产物M@H-TiO2NTs，加入5～15mL0.01-0.1mol/L金属盐水溶液在60～80℃水浴条件下搅拌15～40min，滴加0.5wt％氨水、0.01M氢氧化钠、0.01M氢氧化钾中的一种或多种，搅拌60min，沉降过滤并在烘箱中烘干，然后转移至坩埚中，并于管式炉在氩气气氛中200～300℃退火1～10h得到目标催化剂，记为M@H-TiO2NTs@ROx，M为贵金属，ROx为金属氧化物，金属氧化物包括氧化铜、氧化锰、氧化铁、氧化铋、氧化钴、氧化铈中的一种或多种。
VOCs选自甲苯、乙烯、甲醛等中的任一种。
本发明的有益效果如下：
本发明利用还原态二氧化钛纳米管内腔的微纳空间，将催化活性组元高度分散在还原态二氧化钛纳米管内腔的孔道中，抑制催化剂的团聚和烧结，同时通过表面修饰或改性来进一步调节纳米管内活性组元的氧化性来提高催化性能和稳定性，有利于在光照射条件下高效光催化氧化VOCs转化为二氧化碳和水，本发明得到的高效光催化氧化VOCs的催化剂首先将有机气体分子活化，起燃温度降低，催化燃烧速度加快，大大缩短了处理时间，降低了能耗，提高了效率。
具体实施方式：
以下是对本发明的进一步说明，而不是对本发明的限制。
实施例1：
称量6g P25二氧化钛纳米粉末，将其加入到500mL的聚四氟乙烯瓶中。随后配制10mol/L的氢氧化钠溶液，并用量筒量取360mL溶液加入到装有P25二氧化钛纳米的聚四氟乙烯瓶中，剧烈搅拌半个小时，将聚四氟乙烯瓶放置在油浴中，升温至120℃，回流反应48h。自然冷却至室温，过滤，用去离子水将所制备的粉体洗至接近中性后，用0.1mol/L的盐酸浸泡8小时，之后再用去离子水洗至pH等于7，过滤后将所得的粉体60℃干燥24h，然后在马弗炉中焙烧，升温速率为1℃/min，升温至250℃，保温2h，得到二氧化钛纳米管。
称取0.5g二氧化钛纳米管于100mL聚四氟乙烯内胆反应釜中，将50mL配制好的0.5M硼氢化钠水溶液加入到反应釜中，反应时间为120min。将反应后的产物抽滤后并用去离子水和乙醇清洗多次，最后放置于60℃烘箱中干燥10h得到还原态二氧化钛纳米管产物，标记为H-TiO2NTs。
称取800mg的还原态二氧化钛纳米管H-TiO2NTs或二氧化钛纳米管于100mL的圆底烧瓶中，将量取好的2mL氯铂酸乙醇溶液(1g PtCl4/200mL C2H5OH)分多次滴加到圆底烧瓶中，每次滴加至烧瓶中的粉体刚好浸湿为止，并将其放置于超声中用真空泵在负压下抽干。最后，将催化剂转移至坩埚中，并于管式炉在含有氢气的混合气氛(8％氢气，92％氩气)中200℃退火2h。产物标记为Pt@H-TiO2NTs或Pt@TiO2NTs。
称取400mg的Pt@H-TiO2NTs或Pt@TiO2NTs于100mL的圆底烧瓶中，将量取好的5mL0.1M FeCl3水溶液滴加到圆底烧瓶中，在60℃水浴条件下搅拌20min，滴加少量0.5wt％氨水搅拌60min，沉降过滤并在烘箱中烘干，最后，将催化剂转移至坩埚中，并于管式炉在氩气气氛中200℃退火3h。产物标记为Pt@H-TiO2NTs@Fe2O3或Pt@TiO2NTs@Fe2O3。
将100mg Pt@H-TiO2NTs、Pt@H-TiO2NTs@Fe2O3、Pt@TiO2NTs@Fe2O3分别装载在光催化反应器中，甲苯气体的浓度为150ppm,流速为100mL/min,在300W氙灯照射下，甲苯气体在Pt@H-TiO2NTs上的即时处理效率为75％以上，甲苯气体在Pt@H-TiO2NTs@Fe2O3上的即时处理效率为90％以上，甲苯气体在Pt@TiO2NTs@Fe2O3上的即时处理效率为40％以上。
实施例2
称量6g P25二氧化钛纳米粉末，将其加入到500mL的聚四氟乙烯瓶中。随后配制10mol/L的氢氧化钠溶液，并用量筒量取360mL溶液加入到装有P25二氧化钛纳米的聚四氟乙烯瓶中，剧烈搅拌半个小时，将聚四氟乙烯瓶放置在油浴中，升温至110℃，冷凝回流反应36h。自然冷却至室温，过滤，用去离子水将所制备的粉体洗至接近中性后，用0.1mol/L的盐酸浸泡8小时，之后再用去离子水洗至pH等于7，过滤后将所得的粉体70℃干燥36h。然后在马弗炉中焙烧，升温速率为1℃/min，升温至250℃，保温2h，得到二氧化钛纳米管。
称取0.5g二氧化钛纳米管于100mL聚四氟乙烯内胆反应釜中，将50mL配制好的0.5M硼氢化钠水溶液加入到反应釜中，反应时间为150min。将反应后的产物抽滤后并用去离子水和乙醇清洗多次，最后放置于60℃烘箱中干燥10h。产物标记为H-TiO2NTs。
称取300的H-TiO2NTs或二氧化钛纳米管于100mL的圆底烧瓶中，将量取好的2mL氯金酸乙醇溶液(1gAuCl4/200mL C2H5OH)分多次滴加到圆底烧瓶中，每次滴加至烧瓶中的粉体刚好浸湿为止，并将其放置于超声中用真空泵在负压下抽干。最后，将催化剂转移至坩埚中，并于管式炉在含有氢气的混合气氛(8％氢气，92％氩气)中200℃退火2h。产物标记为Au@H-TiO2NTs或Au@TiO2NTs。
称取400mg的Au@H-TiO2NTs或Au@TiO2NTs于100mL的圆底烧瓶中，将量取好的5mL0.01M Bi(NO)3和5mL 0.01M Cu(NO)2水溶液滴加到圆底烧瓶中，在60℃水浴条件下搅拌30min，滴加少量0.01M氢氧化钠搅拌60min，沉降过滤并在烘箱中烘干，最后，将催化剂转移至坩埚中，并于管式炉在氩气气氛中200℃退火3h。产物标记为Au@H-TiO2NTs@CuO-Bi2O3或Au@TiO2NTs@CuO-Bi2O3。
将100mgAu@H-TiO2NTs、Au@H-TiO2NTs@CuO-Bi2O3、Au@TiO2NTs@CuO-Bi2O3分别装载在光催化反应器中，乙烯气体的浓度为200ppm，流速为150mL/min,在300W氙灯照射下，乙烯气体在Au@H-TiO2NTs上的即时处理效率为80％，而在Au@H-TiO2NTs@CuO-Bi2O3上的即时处理效率为95％以上。在Au@TiO2NTs@CuO-Bi2O3上的即时处理效率为60％以上。
实施例3
称量6g P25二氧化钛纳米粉末，将其加入到500mL的聚四氟乙烯瓶中。随后配制10mol/L的氢氧化钠溶液，并用量筒量取360mL溶液加入到装有P25二氧化钛纳米的聚四氟乙烯瓶中，剧烈搅拌半个小时，将聚四氟乙烯瓶放置在油浴中，升温至115℃，冷凝回流反应36h。自然冷却至室温，过滤，用去离子水将所制备的粉体洗至接近中性后，用0.1mol/L的盐酸浸泡8小时，之后再用去离子水洗至pH约等于7，过滤后将所得的粉体65℃干燥24h然后在马弗炉中焙烧，升温速率为1℃/min，升温至260℃，保温2h，得到二氧化钛纳米管。
称取0.5g二氧化钛纳米管放置于焙烧坩埚中，随后将其放置于气氛炉中，在氢气气氛下焙烧，反应温度为200℃，反应时间为120min。反应后冷却到室温，产物标记为H-TiO2NTs。
称取300的H-TiO2NTs或二氧化钛纳米管于100mL的圆底烧瓶中，将量取好的2mL氯金酸乙醇溶液(1gAuCl4/200mL C2H5OH)和1mL氯化钯乙醇溶液(1g Pd(NO)2/200mL C2H5OH)分多次滴加到圆底烧瓶中，每次滴加至烧瓶中的粉体刚好浸湿为止，并将其放置于超声中用真空泵在负压下抽干。最后，将催化剂转移至坩埚中，并于管式炉在含有氢气的混合气氛(8％氢气，92％氩气)中200℃退火2h。产物标记为Au-Pd@H-TiO2NTs或Au-Pd@TiO2NTs。
称取400mg的Au-Pd@H-TiO2NTs或Au-Pd@TiO2NTs于100mL的圆底烧瓶中，将量取好的5mL 0.01M Bi(NO)3水溶液滴加到圆底烧瓶中，在60℃水浴条件下搅拌30min，滴加少量0.01M氢氧化钠搅拌60min，沉降过滤并在烘箱中烘干，最后，将催化剂转移至坩埚中，并于管式炉在氩气气氛中200℃退火3h。产物标记为Au-Pd@H-TiO2NTs@Bi2O3或Au-Pd@TiO2NTs@Bi2O3。
将100mg Au-Pd@H-TiO2NTs、Au-Pd@H-TiO2NTs@Bi2O3或Au-Pd@TiO2NTs@Bi2O3分别装载在光催化反应器中，甲醛气体的浓度为250ppm，流速为150mL/min,在300W氙灯照射下，甲醛气体在Au-Pd@H-TiO2NTs上的即时处理效率为85％，而在Au-Pd@H-TiO2NTs@Bi2O3上的即时处理效率为98％。而在Au-Pd@TiO2NTs@Bi2O3上的即时处理效率为70％。
Claims (2)
1.一种催化剂在高效光催化氧化VOCs的应用，其特征在于，所述催化剂的制备方法包括以下步骤：
1）水热法制备二氧化钛纳米管：将二氧化钛纳米粉加入到9-15 moL/L的氢氧化钠溶液中，100~180℃搅拌下进行水热反应24~48 h，自然冷却到室温，过滤、去离子水洗涤至洗液pH为7，将0.1~0.5 moL/L的盐酸溶液加入到所得粉体中，搅拌5~10 h，再次用去离子水洗涤至洗液pH为7，过滤，最后将所得粉体在60~100℃条件下干燥24 -36h，然后在马弗炉中焙烧，升温速率为0.5~1 ℃/min，升温至200~400 ℃，保温1~10 h，得到二氧化钛纳米管，记为TiO2NTs；
2）还原二氧化钛纳米管：二氧化钛纳米管用0.5~2 M硼氢化钠水溶液还原反应5~720min，将反应后的产物抽滤后并用去离子水和乙醇清洗多次，最后放置于60~100 ℃烘箱中干燥10~20 h得到还原态二氧化钛纳米管；或，二氧化钛纳米管放置于焙烧坩埚中，随后将其放置于气氛炉中，在氢气气氛下焙烧，反应温度为200~300 ℃，反应时间为60~720 min，反应后冷却到室温得到还原态二氧化钛纳米管，记为H-TiO2NTs；
3）真空辅助超声等体积浸渍法将活性组元贵金属内嵌于还原态二氧化钛纳米管：称取300~800 mg还原态二氧化钛纳米管，将2~10 mL0.005g/mL贵金属乙醇溶液分多次滴加，每次滴加至粉体刚好浸湿为止，并将其放置于超声中用真空泵在负压下抽干，然后转移至坩埚中，并于管式炉在含有8 %氢气和92 %氩气的混合气氛中200~300 ℃退火1~10 h得到催化氧化活性组元贵金属内嵌于还原态二氧化钛纳米管的产物，记为M@H-TiO2NTs，其中M为活性组元贵金属，贵金属包括铂、钯、金、钌、银中的一种或多种；
4）化学沉积法在表面负载金属氧化物催化助剂进行表面修饰：称取300~800 mg步骤3）得到的产物M@H-TiO2NTs，加入5~15 mL0.01-0.1mol/L金属盐水溶液在60~80 ℃水浴条件下搅拌15~40 min，滴加0.5 wt%氨水、0.01M氢氧化钠溶液、0.01M氢氧化钾溶液中的一种或多种，搅拌60 min，沉降过滤并在烘箱中烘干，然后转移至坩埚中，并于管式炉在氩气气氛中200~300 ℃退火1~10 h得到目标催化剂，记为M@H-TiO2NTs@ROx，M为贵金属，ROx为金属氧化物，金属氧化物包括氧化铜、氧化锰、氧化铁、氧化铋、氧化钴、氧化铈中的一种或多种。
2.根据权利要求1所述的应用，其特征在于，VOCs选自甲苯、乙烯、甲醛中的任一种。
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