CN110252365A - 空气产生氢氧根自由基的催化体系及其应用 - Google Patents
空气产生氢氧根自由基的催化体系及其应用 Download PDFInfo
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- CN110252365A CN110252365A CN201910341552.1A CN201910341552A CN110252365A CN 110252365 A CN110252365 A CN 110252365A CN 201910341552 A CN201910341552 A CN 201910341552A CN 110252365 A CN110252365 A CN 110252365A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- PNVJTZOFSHSLTO-UHFFFAOYSA-N Fenthion Chemical compound COP(=S)(OC)OC1=CC=C(SC)C(C)=C1 PNVJTZOFSHSLTO-UHFFFAOYSA-N 0.000 description 2
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
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- 238000006303 photolysis reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920000136 polysorbate Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
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- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
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- MXEJFXMHLHQKRP-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Pb++] Chemical compound [O--].[O--].[Ti+4].[Pb++] MXEJFXMHLHQKRP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
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- C11D3/12—Water-insoluble compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/12—Water-insoluble compounds
- C11D3/1233—Carbonates, e.g. calcite or dolomite
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- C—CHEMISTRY; METALLURGY
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/1266—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in liquid compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2079—Monocarboxylic acids-salts thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
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- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/04—Pesticides, e.g. insecticides, herbicides, fungicides or nematocides
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
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Abstract
一种空气产生氢氧根自由基的催化体系，其特征在于该催化体系以多孔陶瓷为载体，以过渡金属元素为催化中心，以镧元素为催化助剂。本发明还公开了催化体系在水果和蔬菜的残留农药清洗中应用。本发明涉及的催化体系以空气为原料，在室温下能将空气中的氧产生氢氧根自由基，是一种非常稳定的异项催化体系，制备较为简单，使用过程安全无污染。
Description
技术领域
本发明涉及一种氢氧根自由基的产生的材料，本发明还涉及这种材料在清洗农药残留中的应用。
背景技术
农药的发明和使用，大幅提高了粮食、蔬菜、水果等人类生存必需品的产量。但是，由于使用的不当，导致不少收获的粮食、蔬菜、水果等含有较高量的农药残留。这些农药残留虽然有利于产品的保存，但是对人类的健康有害，包括急性的头痛、呕吐，和长期性的癌症、生殖障碍、内分泌失调等(参阅Food Control，2010,21,36-44)。2018年发表的市场抽查结果显示，中国国内的蔬菜农药残留率达到41.9％(参阅Journal of Food Protection,2018,81,377-385)。食用前的清洗成为大幅减少人体农药摄入量的关键，但是，已知的清洗技术，如放射线照射、臭氧处理、双氧水洗涤、等，需要严格控制使用环境和使用的量，只适合大规模的商业化应用，无法在单个的家庭里使用。而蔬菜和水果，是家庭生活的必备，市场上许多的清洗液其成分本身就对人体有害，找到有效的无二次污染的蔬菜水果清洗方法，极其重要。
氢氧根自由基(.0H)具有极强的氧化性，氧化还原电位2.80V，可以无选择性的氧化降解绝大多数环境污染物，包括各种农药残留，这些污染物被氧化的终端产物是无害的物质如水、氮气、无机盐和二氧化碳。已知产生氢氧根自由基的方法较多，大致可分以为化学催化、臭氧/双氧水光解、光催化、超声波臭氧降解、电催化、等离子体(Plasma)电晕(Corona)法、以及射线法等，这些方法都存在安全风险，无法在单个的家庭使用。
化学催化法采用的Fenton反应，铁离子催化双氧水分解产生氢氧根自由基，铁离子物质和双氧水的存储存在安全风险，并且产生铁淤泥二次污染；臭氧和双氧水在紫外光的作用下发生光解，产生氢氧根自由基。相关文献可以参考US8313619B2，还可以参考申请号为200380108146.8的中国发明专利申请公开《增强的氢氧自由基的生成》(公告号:CN1732136A)，再可以参考申请号为201611087121.X的中国发明专利申请公开《一种催化臭氧与气相双氧水/水生成羟基自由基的催化剂及其应用》(公告号:CN106582808A)。但是臭氧对人体有害，需要严格控制使用条件和环境，家庭里难以做到。
二氧化钛颗粒等作为催化剂光催化产生氢氧根自由基，需保证催化剂处于悬浮状态，二氧化钛导致二次污染，紫外光对人体有害；电催化产生氢氧根自由基的方法对水中的溶解氧以及其催化成分要求较高，水中有电对家庭是重大安全问题；等离子体电晕法产生的氢氧根自由基属于高压放电，极不安全，另外，等离子体电晕法因为同时产生氧化氮，氧化氮对人体伤害很大，相关文献可以参考申请号为201410612133.4的中国发明专利申请公开《一种超声雾化辅助电离放电生成氢氧自由基的方法》(公告号:CN104437300A)；射线法则存在成本较高、对人体危害较大的问题；利用有机膜产生氢氧根自由基(US20180162747A1)，属于电解技术，无法家用。
发明内容
本发明所要解决的技术问题是针对上述的技术现状而提供一种以空气为原料无需氢氧根自由基的前体的空气产生氢氧根自由基的催化体系。
本发明所要解决的又一个技术问题是提供一种能在室温下转化空气中氧气的产生氢氧根自由基的催化体系。
本发明所要解决的又一个技术问题是提供一种非常稳定的异相催化的空气产生氢氧根自由基的催化体系。
本发明所要解决的又一个技术问题是提供一种空气产生氢氧根自由基的催化体系的应用。
本发明解决上述技术问题所采用的技术方案为：一种空气产生氢氧根自由基的催化体系，其特征在于该催化体系以多孔陶瓷为载体，以过渡金属元素为催化中心，以镧元素为催化助剂。
作为优选，过渡金属在催化剂中的含量介于0.5-10wt％,镧元素的含量为0.01-1wt％。
作为优选，所述的多孔泡沫陶瓷为开孔泡沫陶瓷，是以氧化铝和高岭土为原材料造出的开孔泡沫陶瓷，其中氧化铝的含量超过60wt％。以氧化铝和高岭土为主要原料的泡沫陶瓷材料，市场上比较成熟的产品，目前用于水质净化居多。
作为优选，所述多孔陶瓷的孔隙在2～50nm之间的介孔材料，气体通过这些孔隙后产生的气泡直径在0.5-20微米之间，气孔率为30-50％。优选用于过滤净化水的过滤用多孔陶瓷。
所述的过渡金属元素可以是Mn、Fe、Cu、Ni、Co、Ru、Rh中的至少一种。
所述的过渡金属元素优选采用如下之一的方式上载到多孔陶瓷上：
第一种，将过渡金属元素的可溶性化合物溶解在水中制备为饱和的水溶液，将多孔陶瓷浸泡在水溶液中4个小时或4小时以上，取出浸泡好的多孔陶瓷，烘干；
第二种，将水不溶性过渡金属元素的氧化物配制为饱和的悬浮乳浊液，将多孔陶瓷浸泡在水溶液中4个小时或4小时以上，取出浸泡好的多孔陶瓷，烘干。
所述镧元素优选采用如下之一的方式上载到多孔陶瓷上：
第一种，将镧元素的可溶性化合物溶解在水中制备为饱和的水溶液，将多孔陶瓷浸泡在水溶液中4个小时或4小时以上，取出浸泡好的多孔陶瓷，烘干；
第二种，将水不溶性镧元素的氧化物配制为饱和的悬浮乳浊液，将多孔陶瓷板浸泡在水溶液中4个小时或4小时以上，取出浸泡好的多孔陶瓷，烘干。
所述镧元素可以与过渡金属元素一起上载；也可以是分开上载，即镧元素先与过渡金属元素上载，或者过渡金属元素先与镧元素上载。
空气产生氢氧根自由基的催化体系在水果和蔬菜的残留农药清洗中应用。
与现有技术相比，本发明的优点在于：本发明以空气为原料，在室温下能将空气中的氧产生氢氧根自由基，是一种非常稳定的异项催化体系，制备较为简单，使用过程安全无污染，应用于果蔬清洗中，基本上都能将所有的残留农药洗脱掉。
附图说明
图1为催化体系在清洗农药残留中的应用示意图。
具体实施方式
以下结合附图实施例对本发明作进一步详细描述。
实施例1，催化剂的制备
实施例1A，含金属(锰、铁、铜、镍、钴、钌、铑)催化剂的制备：
方法1.将选定的多孔陶瓷板浸泡在1-20wt％的金属硝酸盐(例如硝酸锰)的水溶液中4个小时或更长，然后取出，400℃温度下干燥后，得含有金属催化中心的多孔陶瓷板催化剂，制备得到的催化剂中的金属含量为0.5-10wt％：PM1。
方法2.金属氧化物(例如氧化锰)的纳米粉末，用土温(Tween)作为乳化剂，配制成含量为1-20wt％的水乳浊液，然后将多孔陶瓷板浸泡在乳浊液4个小时或更长，然后取出，400℃温度下干燥后，得含有金属催化中心的多孔陶瓷板催化剂，制备得到的催化剂中的金属含量为0.5-10wt％：PM2。
实施例1B，含金属(锰、铁、铜、镍、钴、钌、铑)和镧的催化剂的制备：
方法1.将选定的多孔陶瓷板浸泡在0.1-5wt％的硝酸镧和1-20wt％的金属硝酸盐(例如硝酸锰)的水溶液中4个小时或更长，然后取出，400℃温度下干燥后，得含有微量镧和金属催化中心的多孔陶瓷板催化剂，制备得到的催化剂中的镧含量为0.01-1wt％,过渡金属含量为0.5-10wt％：PML1。
方法2.金属氧化物(例如氧化锰)的纳米粉末，用土温(Tween)作为乳化剂，配制成含量为0.1-5wt％的硝酸镧、和1-20％的金属氧化物的水乳浊液，然后将多孔陶瓷板浸泡在乳浊液4个小时或更长，然后取出，400℃温度下干燥后，得含有微量镧和金属催化中心的多孔陶瓷板催化剂，制备得到的催化剂中的镧含量为0.01-1wt％,过渡金属含量为0.5-10wt％：PML2。
实施例2，各种催化剂催化空气中氧气为氢氧根自由基(OH)功效的能力实验设置按附图所示的设计，氢氧根自由基采用CCA荧光法，激发光波长400nm，发射光波长检测450nm。试验时，首先通入空气20分钟使水相中的氧气达到饱和，然后再取样测定水相中的7-OH-CCA的浓度来测定氢氧根自由基浓度。水相的pH值使用0.1N的盐酸和0.1N的氢氧化钠进行调节。实施例中使用的催化剂，镧含量为0.1wt％,过渡金属含量为3wt％。虽然它们含量高时(过渡金属10wt％，镧1wt％)的催化效果较高，但是氢氧根自由基的产量最高只增加20％左右，但是低于这个含量时，催化效果下降明显。它们的含量是高限时，催化剂的成本增加不少，所以选用最易于制备的催化剂用于实施例。
实施例3.催化体系去除残留农药的能力
催化剂的催化效果通过去除水果蔬菜上几种具代表性的农药的去除率来测定。
结合图1所示，空气通过空气泵1，经导管2从底部进入洗涤容器3，然后通过多孔陶瓷4以很小的气泡达到洗涤容器3内，这里的多孔陶瓷4做成板状，需要洗涤的水果和蔬菜放置在洗涤容器3内，水面需要超过水果和蔬菜。
残留的农药以氨基甲酸酯(Carbosulfan)、倍硫磷(Fenthion)、和氯氰拟除虫菊酯(Cypermethrin)为代表。水果和蔬菜上的这些残留农药的测定采用AOAC发布的GCMS检测方法(AOAC Official Method of Analysis 2000)。分别选取了较有代表性的西红柿、黄瓜、元白菜、芹菜、葡萄、和大枣。用自来水洗涤，洗除三种农药之和的浓度，鼓风机的速度为3立方米/分钟，洗涤容器体系5升，洗涤的蔬菜或水果都是1公斤，分别测定20分钟和1小时的洗涤效果，如下表所示：
| 西红柿 | 黄瓜 | 元白菜 | 芹菜 | 葡萄 | 大枣 | |
| 洗前浓度(mg/kg) | 0.51 | 0.97 | 1.83 | 4.38 | 3.9 | 1.9 |
| 只鼓风无催化剂洗60分钟(％) | 11.3 | 9.2 | 6.6 | 7.3 | 17.3 | 15.5 |
| 洗20分钟洗除率(％) | 59.8 | 63.2 | 33.6 | 43.1 | 97 | 91.5 |
| 洗60分钟洗除率(％) | 99.6 | 99.3 | 97.9 | 92.7 | 99.9 | 99.9 |
从这些结果可以看出，只用鼓风机鼓风进入洗浴容器，能够洗脱一部分残留农药，但是洗脱率较低；而使用我们发明的催化剂，如果洗60分钟，基本上都能将所有的残留农药洗脱掉，对于人类的健康，本发明以不产生任何二次污染的方法降解去除残留农药的技术，意义重大。
上述实施例中涉及的多孔泡沫陶瓷为开孔泡沫陶瓷，是以氧化铝和高岭土为原材料造出的开孔泡沫陶瓷，其中氧化铝的含量超过60wt％，为成熟产品，市场上容易购得。
Claims (9)
1.一种空气产生氢氧根自由基的催化体系，其特征在于该催化体系以多孔陶瓷为载体，以过渡金属元素为催化中心，以镧元素为催化助剂。
2.根据权利要求1所述的就地生产氢氧根自由基的催化体系，其特征在于所述过渡金属在催化剂中的含量介于0.5-10wt％,镧元素的含量为0.01-1wt％。
3.根据权利要求1所述的就地生产氢氧根自由基的催化体系，其特征在于所述的多孔泡沫陶瓷为开孔泡沫陶瓷，是以氧化铝和高岭土为原材料造出的开孔泡沫陶瓷，其中氧化铝的含量超过60wt％。
4.根据权利要求3所述的空气产生氢氧根自由基的催化体系，其特征在于所述多孔陶瓷的孔隙在2～50nm之间的介孔材料，气体通过这些孔隙后产生的气泡直径在0.5-20微米之间，气孔率为30-50％。
5.根据权利要求1所述的空气产生氢氧根自由基的催化体系，其特征在于所述的过渡金属元素为Mn、Fe、Cu、Ni、Co、Ru、Rh中的至少一种。
6.根据权利要求1所述的空气产生氢氧根自由基的催化体系，其特征在于所述的过渡金属元素采用如下之一的方式上载到多孔陶瓷上：
第一种，将过渡金属元素的可溶性化合物溶解在水中制备为饱和的水溶液，将多孔陶瓷浸泡在水溶液中4个小时或4小时以上，取出浸泡好的多孔陶瓷，烘干；
第二种，将水不溶性过渡金属元素的氧化物配制为饱和的悬浮乳浊液，将多孔陶瓷浸泡在水溶液中4个小时或4小时以上，取出浸泡好的多孔陶瓷，烘干。
7.根据权利要求1所述的空气产生氢氧根自由基的催化体系，其特征在于所述镧元素采用如下之一的方式上载到多孔陶瓷上：
第一种，将镧元素的可溶性化合物溶解在水中制备为饱和的水溶液，将多孔陶瓷浸泡在水溶液中4个小时或4小时以上，取出浸泡好的多孔陶瓷，烘干；
第二种，将水不溶性镧元素的氧化物配制为饱和的悬浮乳浊液，将多孔陶瓷板浸泡在水溶液中4个小时或4小时以上，取出浸泡好的多孔陶瓷，烘干。
8.根据权利要求1所述的空气产生氢氧根自由基的催化体系，其特征在于所述镧元素与过渡金属元素一起上载；或者镧元素先与过渡金属元素上载，或者过渡金属元素先与镧元素上载。
9.权利要求1～8中的所述的空气产生氢氧根自由基的催化体系在水果和蔬菜的残留农药清洗中应用。
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| CN103240092A (zh) * | 2012-02-02 | 2013-08-14 | 浙江海洋学院 | 一种用于渣油加工废水脱臭回用的常温空气湿式氧化催化剂 |
| CN104923229A (zh) * | 2014-03-21 | 2015-09-23 | 中国科学院大连化学物理研究所 | 用于类Fenton技术的活性炭催化剂及其制备和应用 |
| CN104206937A (zh) * | 2014-08-22 | 2014-12-17 | 中国人民解放军总后勤部军需装备研究所 | 一种果蔬表面农残深度处理方法 |
| CN104588127A (zh) * | 2014-10-13 | 2015-05-06 | 宁波市雨辰环保科技有限公司 | 一种催化剂活化方法 |
| CN106807239A (zh) * | 2015-11-27 | 2017-06-09 | 宁波市雨辰环保科技有限公司 | 甲醛为助剂的室温下催化活化氧气清除挥发性有机物的催化体系及其制备方法和应用 |
| CN107185535A (zh) * | 2016-05-31 | 2017-09-22 | 浙江理工大学 | 一种无光除醛催化剂、包含所述催化剂的除醛体系及其用途 |
| CN108669584A (zh) * | 2018-06-01 | 2018-10-19 | 陈遥 | 果蔬清洁装置 |
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