CN113522307B - 一种用于净化空气中有机气体污染物及抑菌的z型异质结光热催化剂 - Google Patents
一种用于净化空气中有机气体污染物及抑菌的z型异质结光热催化剂 Download PDFInfo
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- CN113522307B CN113522307B CN202110707591.6A CN202110707591A CN113522307B CN 113522307 B CN113522307 B CN 113522307B CN 202110707591 A CN202110707591 A CN 202110707591A CN 113522307 B CN113522307 B CN 113522307B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 18
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 18
- 241000894006 Bacteria Species 0.000 title claims abstract description 11
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052709 silver Inorganic materials 0.000 claims abstract description 19
- 239000004332 silver Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000005751 Copper oxide Substances 0.000 claims abstract description 11
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 11
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 8
- 238000012546 transfer Methods 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 239000012265 solid product Substances 0.000 claims description 10
- 229910002367 SrTiO Inorganic materials 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
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- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 239000012691 Cu precursor Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000002211 L-ascorbic acid Substances 0.000 claims description 3
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 25
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 11
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- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 230000002195 synergetic effect Effects 0.000 abstract description 7
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000001954 sterilising effect Effects 0.000 abstract description 4
- 238000004887 air purification Methods 0.000 abstract 1
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- 230000005764 inhibitory process Effects 0.000 description 5
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- 238000006555 catalytic reaction Methods 0.000 description 4
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
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- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
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Abstract
本发明公开了一种用于净化空气中有机气体污染物及抑菌的Z型异质结光热催化剂，由铜的氧化物、银、钛酸锶或二氧化钛组成，其光生电荷呈现Z型传递路径。该异质结催化剂不仅能通过光热协同催化氧化作用净化室内甲醛、甲苯等有机气体污染物，还将银、铜的氧化物的化学消杀抗菌性与光催化抗菌性结合使其具有优异的抗菌性能。该催化剂制备工艺简单、成本较低、适合宏量制备和推广应用于室内空气净化相关领域。
Description
技术领域
本发明涉及一种用于净化空气中有机气体污染物及抑菌的Z型异质结光热催化剂，及其在有机气体污染物净化和抑菌中的应用，属于环境保护技术领域。
背景技术
近年来室内外空气污染问题日益严重，其中挥发性有机化合物(VOCs)就是典型的气体污染物，研发一种绿色低能耗的方式高效去除VOCs是目前亟需解决的难题。为了解决传统光催化低效率及热催化高能耗等问题，国内外研究者们提出了光热协同催化氧化技术，达到比单一光催化或热催化氧化更高的催化活性。光热催化净化空气污染物的关键是开发高效光热催化材料。异质结的构筑是促使载流子在半导体界面的传递与分离的一种有效手段，能显著提高催化效率。相较于传统异质结，Z型异质结独特的电子传输途径使得催化剂在保证电子-空穴分离效率的同时，可增强其氧化还原能力。全固态Z型异质结催化剂通常由两个半导体与接触界面间的电子导体构成。贵金属纳米粒子是最常用的中间电子导体，研究表明贵金属的表面等离子体共振(SPR)效应能有效提高其催化活性。专利ZL201810417799.2提供了一种由TiO2纳米管阵列(TiNT)、AgBr和Ag构成的Z型AgBr/Ag/SrTiO3-TiNT催化剂，对于甲醛、对二甲苯和乙酸乙酯等单体小分子有机物及其混合物都具有一定的催化效能，可用于降解空气中常见的有机污染物。然而催化剂制备流程复杂、Ag负载量过高、催化材料成本高，不易推广应用。
此外，除了甲醛等化学性污染物的净化，室内细菌和病毒等生物污染的防控也逐渐引起人们的关注。研发能够同时去除室内甲醛、苯系物等VOCs化学污染物和杀菌消毒功能的高效多功能环境净化材料和技术关系民生，具有良好的应用前景。目前，纳米抗菌材料，如铜、银、二氧化钛等纳米粒子，的消杀机制主要包括化学消杀以及光催化杀菌机理（活性氧抗菌机理）。纳米材料的化学消杀是利用金属离子破坏微生物细胞膜的通透性从而达到灭菌消毒的效果；而光催化杀菌是基于光催化机理，半导体无机材料光照后产生具有较强氧化性的·OH和·O2 -自由基，自由基与水及细菌进一步作用从而破坏细胞结构。然而，无论化学消杀法还是光催化消杀法，都存在一定的应用局限性、消杀细菌的能力不足。
发明内容
针对上述室内空气VOCs和细菌污染物净化技术所面临的技术难题，本发明公开了一种由铜的氧化物、银、钛酸锶或二氧化钛组成的Z型异质结光热催化剂，其不仅能通过光热协同催化氧化作用高效净化室内甲醛、甲苯等有机气体污染物，还将银、铜的氧化物的化学消杀抗菌性与光催化抗菌性相结合，展现出优异的抗菌性能。
为了实现上述发明目的，本发明采用的技术方案如下：
一种用于净化空气中有机气体污染物及抑菌的Z型异质结光热催化剂，由铜的氧化物、银、钛酸锶或二氧化钛组成的CuOx/Ag/SrTiO3 (或TiO2)异质结构，其光生电荷呈现Z型传递路径。
上述的异质结光热催化剂中，以催化剂的重量为100%计，单质银的重量分数为0.1~5%，铜的氧化物以单质铜的重量级，其重量百分比为0.5%~10%。
上述的异质结光热催化剂的制备方法包括以下步骤：
（1）在钛酸锶或二氧化钛载体上分散在银的前躯体溶液中，利用湿化学还原法在载体上原位沉积负载银；
（2）将步骤1中得到的固体产物干燥后，分散在铜的前躯体溶液，利用碱性条件下的沉积沉淀法负载铜，并通过在过程中加入还原剂调控铜的价态，在惰性气氛干燥后制得异质结光热催化剂。
上述的制备方法，步骤（1）中，所述银的前驱体可以选择AgNO3、Ag(acac)、氯化银中的一种，优选AgNO3；所述二氧化钛载体为锐钛矿、金红石或者金红石与锐钛矿复合矿相结构中的一种；所述钛酸锶(SrTiO3)的制备方法为已有技术，所属领域的技术人员可以根据现有技术中所公开的各种制备方法得到上述载体，示例性方法包括但不限于文献的水热法（Industrial & Engineering Chemistry Research,2016, 55, 11923; Chemical Communications, 2017, 53, 12329），这些文献引入本发明作为参考；所述还原性溶液为硼氢化钠、硼氢化钾或氢化钠的一种或多种，还原剂的添加量与贵金属M的摩尔比例范围为1~100。
上述的制备方法步骤（2）中，所述铜的前驱体可以选择硫酸铜、硝酸铜、醋酸铜或氯化铜中的一种，优选硫酸铜；所述还原剂为L-抗坏血酸、葡萄糖、柠檬酸钠水溶液等水溶液中的任意一种，调控铜的氧化物中Cu+/Cu2+的比例范围为0.01~100，优选0.1~10。
上述的制备方法步骤（2）中，所述催化剂的干燥气氛为氮气或其它惰性气体氛围，干燥温度为80~150 °C。
上述的异质结光热催化剂在去除室内空气中有机气体污染物和细菌中的应用。
与现有技术相比，本发明具有如下有益效果:
本发明制备的用于室内空气VOCs和细菌污染物净化的Z型异质结催化剂，组成和制备方法简单，便于推广应用，可在温和光热条件下催化氧化室内主要VOCs污染物甲醛和甲苯等为二氧化碳和水，和消杀大肠杆菌等典型细菌污染物。适用于去除生产车间、居室、建材家具市场和实验室等封闭、半封闭空间中的空气污染物。
具体实施方式
本发明的实施方法灵活可变，不仅仅限于此例所述的具体操作方式，为更好地说明本发明，便于理解本发明的技术方案，下面结合具体的实施例对本发明作进一步详细的叙述。
实施例1
取0.5 g钛酸锶粉末超声分散于30 mL去离子水中，在剧烈搅拌下，按目标产物中银的负载量为1wt.%计，逐滴加入适量的硝酸银的水溶液，然后按还原剂的添加量与Ag的摩尔比为4的量，加入硼氢化钠水溶液，继续搅拌4 h，离心分离后分别用去离子水和无水乙醇多次洗涤固体产物，80°C烘箱中干燥后得到固定产物Ag/SrTiO3。将Ag/SrTiO3粉末与按目标产物中Cu的负载量为5 wt.%计所需一定量的硫酸铜加入到60 mL的0.2 mol/L 的NaOH水溶中，搅拌0.5 h，然后按目标产物里铜的氧化物中Cu+/Cu2+的摩尔比例为~1的需求逐滴加入一定量0.1 mol/L的L-抗坏血酸水溶液调控铜元素价态。搅拌0.5 h后，通过离心分离法收集产物，并分别用去离子水和无水乙醇洗涤固体产物，在80 °C的N2的氛围下干燥，得到Z型异质结光热催化材料CuOx/Ag/SrTiO3。
实施例2
取0.5 g锐钛矿型TiO2粉末超声分散于30 mL去离子水中，在剧烈搅拌下，按目标产物中银的负载量为3wt.%计，逐滴加入适量的醋酸银的水溶液，然后按还原剂的添加量与Ag的摩尔比为20的量，加入硼氢化钾水溶液，继续搅拌4 h，离心分离后分别用去离子水和无水乙醇多次洗涤固体产物，80 °C烘箱中干燥后得到固定产物Ag/TiO2。将Ag/TiO2粉末与按目标产物中Cu的负载量为8 wt.%计所需一定量的硝酸铜加入到60 mL 的0.2 mol/L 的NaOH水溶中，搅拌0.5 h，然后按目标产物里铜的氧化物中Cu+/Cu2+的摩尔比例为~0.5的需求逐滴加入一定量的0.1 mol/L 柠檬酸钠水溶液调控铜元素价态。搅拌0.5 h后，通过离心分离法收集产物，并分别用去离子水和无水乙醇洗涤固体产物，在100°C的N2的氛围下干燥，得到Z型异质结光热催化材料CuOx/Ag/TiO2。
实施例3
取0.5 gP25（锐钛矿型TiO2和金红石型TiO2以4:1摩尔比例混合组成）粉末超声分散于30 mL去离子水中，在剧烈搅拌下，按目标产物中银的负载量为0.5 wt.%计，逐滴加入适量的硝酸银的水溶液，然后按还原剂的添加量与Ag的摩尔比为50的量，加入硼氢化钠水溶液，继续搅拌4 h，离心分离后分别用去离子水和无水乙醇多次洗涤固体产物，80 °C烘箱中干燥后得到固定产物Ag/SrTiO3。将Ag/ P25粉末与按目标产物中Cu的负载量为3 wt.%计所需一定量的硫酸铜加入到60 mL 的0.2 mol/L 的NaOH水溶中，搅拌0.5 h，然后按目标产物里铜的氧化物中Cu+/Cu2+的摩尔比例为~5的需求逐滴加入一定量的0.1 mol/L的葡萄糖水溶液调控铜元素价态。搅拌0.5 h后，通过离心分离法收集产物，并分别用去离子水和无水乙醇洗涤固体产物，在120 °C的氩气的氛围下干燥，得到Z型异质结光热催化材料CuOx/Ag/P25。
实施例4
分别取实施例1~3中的样品约0.2 g涂在7.0 cm2石英培养皿上，置于反应器底部。通过将模拟空气(O2∶N2 = 1:3)以一定的流速流动到甲醛或甲苯液体中进行鼓泡，将甲醛或甲苯气体注入到反应容器中，将VOCs的初始浓度调控至约600~1000 ppm。在达到吸附-解吸平衡并在温度保持恒定后进行反应测试，打开带有420 nm紫外截止滤光片的氙灯。在光电流密度为100 mW·cm-2，初始压力为0.5 MPa的条件下进行催化反应。在反应过程中，一定时间间隔用取气针取出约1 mL气体混合物，然后分别用GC2030和GC1690气相色谱仪分析气体中甲醛/甲苯和二氧化碳的含量并用于换算甲醛/甲苯的消除率。光热协同净化VOCs性能列于表1。
实施例5
分别取实施例1~2中的样品约0.001g制成1mg/mL的溶液，溶剂选择二甲亚砜，菌种选择大肠杆菌，通过牛津杯扩散法来评价催化剂的抗菌性能。取溶剂作为对照组。将样品、实验器材等在超净工作台紫外消毒至少15min。在固体培养基上涂抹100 μL的细菌培养液（OD值为0.9~1.1，优选1.1），然后将牛津杯轻放在固体培养基表面，轻轻加压使其与培养基紧密接触。最后取200 μL样品溶液加入到牛津杯中。培养皿在37°C下培养24 h，抗菌活性通过抑菌圈的大小来估计。实验在相同条件下重复3次，用酶标仪测试大肠杆菌OD值(opticaldensity，光密度，1OD≈108~109cfu/mL,即108~109个菌体/mL) 。测试结果列于表2。
表1 异质结催化剂光热协同净化VOCs性能
表2异质结催化剂光热协同消杀大肠杆菌的性能
附表说明
表1：
从表1可以看出，实施例1-3制备的Z型异质结光热催化剂均具有良好的光热协同催化净化甲苯或甲醛的催化活性。其中，在90 °C和可见光照射下，实施例1所合成的异质结催化剂CuOx/Ag/SrTiO3在40 min内催化降解甲苯的转化率均超过99%。
表2：
从表2可以看出，实施例1-2制备的Z型异质结光热催化剂均具有良好的光热协同消杀大肠杆菌的性能，与空白对照处的抑菌圈相比，涂有催化剂处的抑菌圈明显增大20%左右，说明所开发的样品具有明显的抑菌效果。
Claims (5)
1.一种用于净化空气中有机气体污染物及抑菌的Z型异质结光热催化剂，其特征在于，该催化剂由铜的氧化物、银、钛酸锶或二氧化钛组成CuOx/Ag/SrTiO3(或TiO2)异质结构；其光生电荷呈现Z型传递路径；以催化剂的重量为100％计，单质银的重量分数为0.1～5％，铜的氧化物以单质铜的重量级，其重量百分比为0.5％～10％。
2.如权利要求1所述异质结光热催化剂的制备方法包括以下步骤：
(1)在钛酸锶或二氧化钛载体上分散在银的前躯体溶液中，利用湿化学还原法在载体上原位沉积负载银；
(2)将步骤1中得到的固体产物干燥后，分散在铜的前躯体溶液，利用碱性条件下的沉积沉淀法负载铜，并通过在过程中加入还原剂调控铜的价态，在惰性气氛干燥后制得异质结光热催化剂。
3.如权利要求2所述的制备方法，其特征在于所述步骤(1)中，所述银的前驱体可以选择AgNO3、Ag(acac)、氯化银中的一种；还原性溶液为硼氢化钠、硼氢化钾或氢化钠的一种或多种，还原剂的添加量与贵金属M的摩尔比例范围为1～100。
4.如权利要求2所述的制备方法，其特征在于所述步骤(2)中所述铜的前驱体可以选择硫酸铜、硝酸铜、醋酸铜或氯化铜中的一种；所述还原剂为L-抗坏血酸、葡萄糖、柠檬酸钠水溶液水溶液中的任意一种，调控铜的氧化物中Cu+/Cu2+的比例范围为0.01～100。
5.权利要求1-4所述的异质结光热催化剂在去除空气中有机气体污染物和细菌中的应用。
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