CN113856664B - 镧系金属掺杂TiO2中空纳米盒子催化剂及其制备方法、应用 - Google Patents
镧系金属掺杂TiO2中空纳米盒子催化剂及其制备方法、应用 Download PDFInfo
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- 229910052747 lanthanoid Inorganic materials 0.000 title claims abstract description 29
- 150000002602 lanthanoids Chemical class 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 24
- 239000002184 metal Substances 0.000 title claims abstract description 24
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000000575 pesticide Substances 0.000 claims abstract description 13
- 230000009920 chelation Effects 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 20
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- 238000010438 heat treatment Methods 0.000 claims description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 10
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 8
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 8
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 claims description 8
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- 238000004090 dissolution Methods 0.000 claims description 8
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
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- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 3
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 15
- 239000011941 photocatalyst Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
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- 229910052761 rare earth metal Inorganic materials 0.000 description 5
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- ZNOLGFHPUIJIMJ-UHFFFAOYSA-N fenitrothion Chemical compound COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C(C)=C1 ZNOLGFHPUIJIMJ-UHFFFAOYSA-N 0.000 description 2
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- YFGYUFNIOHWBOB-UHFFFAOYSA-N pirimicarb Chemical compound CN(C)C(=O)OC1=NC(N(C)C)=NC(C)=C1C YFGYUFNIOHWBOB-UHFFFAOYSA-N 0.000 description 2
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 2
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- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
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- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
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- 230000005525 hole transport Effects 0.000 description 1
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- 229940056881 imidacloprid Drugs 0.000 description 1
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- -1 lanthanide metals Chemical class 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
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- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 1
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- LLZBVBSJCNUKLL-UHFFFAOYSA-N thulium(3+);trinitrate Chemical compound [Tm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LLZBVBSJCNUKLL-UHFFFAOYSA-N 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种镧系金属掺杂TiO2中空纳米盒子催化剂的制备方法，首先获得镧系金属离子掺杂的CaTiO3立方体，再通过鳌合反应原位转化成了镧掺杂的TiO2，最后通过煅烧获得具有稳定晶型的空心盒子。本发明通过形貌调控制得具有空心盒子状结构的TiO2，具有较大的比表面积，同时镧系金属离子掺杂减少了光生载流子的复合，使催化剂具有更高的催化活性，具有高活性、低成本、操作简单、安全、重复性强、操作工艺参数易控的优点，能够对新烟碱类农药进行有效处理，避免二次污染。
Description
【技术领域】
本发明属于纳米材料和光催化技术领域，涉及一种镧系金属掺杂TiO2中空纳米盒子催化剂极其制备方法、应用。
【背景技术】
农药作为一种化学品被大量应用于农业领域，但是农药的过度利用对水源、土壤都造成污染，并且这些有机污染物可以在生物组织中累积，给人类和动物的健康都造成了严重威胁。吡啶虫胺与吡虫啉都属于新烟碱类高效杀虫剂，是世界上使用最广泛的杀虫剂，但因其在水中的溶解度较高、容易积累，并且在环境中难以自我降解等问题而引起了广泛关注。因此寻找一种有效的方法来减轻新烟碱类农药的残留与积累显得尤为重要。
在以往的研究中可知，已探索出多种解决新烟碱类农药残留和累积的方法。其中主要的方法有微生物降解法、电催化法、等离子技术等。但是这些方法普遍存在着成本高、能耗高、易受环境影响且容易造成二次污染等缺点。
【发明内容】
为了解决上述问题，本发明提供一种高活性、低成本、操作简单、安全、重复性强、操作工艺参数易控的掺杂镧系金属的TiO2中空纳米盒子催化剂，其能够对新烟碱类农药进行有效处理，避免二次污染。
本发明是通过以下技术方案实现的，提供一种镧系金属掺杂TiO2中空纳米盒子催化剂的制备方法，包括以下步骤：
S1将0.44g二水合氯化钙溶解于12～16ml聚乙二醇-200及40～50ml无水乙醇的混合溶剂中，混合均匀，获得混合溶液一，在搅拌状态下加入镧系水合硝酸盐至上述混合溶液一中搅拌均匀，随后加入钛酸四丁酯，完全溶解后加入0.9～1g的氢氧化钠搅拌1h，获得混合物；
S2将S1得到混合物转移至100ml高压反应釜中，在180℃下反应12～16h冷却至室温后，将所得产物分别用去离子水和无水乙醇洗涤干净，烘干研磨，获得样品；
S3取0.3gS2所得的样品溶解于12～16ml乙二醇及40～50ml去离子水混合溶剂中，搅拌均匀后加入1.2～1.4g的EDTA-2Na，搅拌均匀后转移到100ml高压反应釜中，在180℃烘箱中反应12～16h，鳌合反应结束后冷却至室温；
S4分别用无水乙醇和去离子水真空抽滤洗涤，之后在烘箱中干燥，充分研磨后转入马弗炉中加热，即得镧系金属掺杂TiO2中空纳米盒子催化剂。
特别的，所述S1中钛酸四丁酯、镧系水合硝酸盐的摩尔比为20：1。
特别的，所述S3中乙二醇、去离子水的体积比为1:3。
特别的，所述S4中转入马弗炉中加热以5℃/min的升温速率升至400℃后保持2h。
本发明还提供一种采用上述方法制备的镧系金属掺杂TiO2中空纳米盒子催化剂，所述掺杂的金属为La、Ce、Sm、Yb、Tm中的至少一种。
本发明还提供一种镧系金属掺杂TiO2中空纳米盒子催化剂在新烟碱类农药降解中的应用。
本发明提供一种镧系金属掺杂TiO2中空纳米盒子催化剂的制备方法，利用自牺牲模板法合成了具有中空分层立方盒子形貌的TiO2，首先获得镧系金属离子掺杂的CaTiO3立方体，再通过鳌合反应原位转化成了镧掺杂的TiO2，最后通过煅烧获得具有稳定晶型的空心盒子。本发明通过形貌调控制得具有空心盒子状结构的TiO2，具有较大的比表面积，同时镧系金属离子掺杂减少了光生载流子的复合，使催化剂具有更高的催化活性。
【附图说明】
图1为本发明一种镧系金属掺杂TiO2中空纳米盒子催化剂的的XRD图谱；
图2为本发明实施例的扫描电子显微镜图片；
图3为本发明实施例的透射电子显微镜图片；
图4为本发明实施例的光催化降解效果图。
【具体实施方式】
为了使本发明的目的、技术方案及优点更加清楚明白，以下分为两组进行实验，其中第一组为实施例组，为实施例1-6，另一组为实验组，为实施例7-12，分别对各实施例中所制得催化剂做活性测试。
实施例1
将0.44g二水合氯化钙溶解于15ml聚乙二醇-200及45ml无水乙醇的混合溶剂中，混合均匀，在不断搅拌下缓慢加入1.32ml钛酸四丁酯，完全溶解后加入0.96g的氢氧化钠搅拌1h。将得到混合物转移到100ml高压反应釜中在180℃下反应15h，冷却后将所得产物分别用去离子水和无水乙醇洗涤三次，烘干研磨后取0.3g样品溶解于15ml乙二醇及45ml去离子水混合溶剂中，搅拌均匀后加入1.36g的EDTA-2Na，混合溶液搅拌均匀后转移到100ml高压反应釜中，在180℃烘箱中分别反应15h，鳌合反应结束后冷却至室温，分别用无水乙醇和去离子水真空抽滤洗涤，得到的样品在烘箱中干燥，充分研磨后转入马弗炉中，以5℃/min的升温速率升至400℃保持2h，即得TiO2-15复合纳米光催化剂。
实施例2
将0.44g二水合氯化钙溶解于15ml聚乙二醇-200及45ml无水乙醇的混合溶剂中，混合均匀，在不断搅拌下按钛：镧摩尔比为20：1加入0.0840g硝酸镧至上述混合溶液中搅拌均匀，随后缓慢加入1.32ml钛酸四丁酯，完全溶解后加入0.96g的氢氧化钠搅拌1h。将得到混合物转移到100ml高压反应釜中在180℃下反应15h，冷却后将所得产物分别用去离子水和无水乙醇洗涤三次，烘干研磨后取0.3g样品溶解于15ml乙二醇及45ml去离子水混合溶剂中，搅拌均匀后加入1.36g的EDTA-2Na，混合溶液搅拌均匀后转移到100ml高压反应釜中，在180℃烘箱中分别反应15h，鳌合反应结束后冷却至室温，分别用无水乙醇和去离子水真空抽滤洗涤，得到的样品在烘箱中干燥，充分研磨后转入马弗炉中，以5℃/min的升温速率升至400℃保持2h，即得La-TiO2-15复合纳米光催化剂。
实施例3
将0.44g二水合氯化钙溶解于15ml聚乙二醇-200及45ml无水乙醇的混合溶剂中，混合均匀，在不断搅拌下按钛：铈摩尔比为20：1加入0.0842g硝酸铈至上述混合溶液中搅拌均匀，随后缓慢加入1.32ml钛酸四丁酯，完全溶解后加入0.96g的氢氧化钠搅拌1h。将得到混合物转移到100ml高压反应釜中在180℃下反应15h，冷却后将所得产物分别用去离子水和无水乙醇洗涤三次，烘干研磨后取0.3g样品溶解于15ml乙二醇及45ml去离子水混合溶剂中，搅拌均匀后加入1.36g的EDTA-2Na，混合溶液搅拌均匀后转移到100ml高压反应釜中，在180℃烘箱中分别反应15h，鳌合反应结束后冷却至室温，分别用无水乙醇和去离子水真空抽滤洗涤，得到的样品在烘箱中干燥，充分研磨后转入马弗炉中，以5℃/min的升温速率升至400℃保持2h，即得Ce-TiO2-15复合纳米光催化剂。
实施例4
将0.44g二水合氯化钙溶解于15ml聚乙二醇-200及45ml无水乙醇的混合溶剂中，混合均匀，在不断搅拌下按钛：钐摩尔比为20：1加入0.0845g硝酸钐至上述混合溶液中搅拌均匀，随后缓慢加入1.32ml钛酸四丁酯，完全溶解后加入0.96g的氢氧化钠搅拌1h。将得到混合物转移到100ml高压反应釜中在180℃下反应15h，冷却后将所得产物分别用去离子水和无水乙醇洗涤三次，烘干研磨后取0.3g样品溶解于15ml乙二醇及45ml去离子水混合溶剂中，搅拌均匀后加入1.36g的EDTA-2Na，混合溶液搅拌均匀后转移到100ml高压反应釜中，在180℃烘箱中分别反应15h，鳌合反应结束后冷却至室温，分别用无水乙醇和去离子水真空抽滤洗涤，得到的样品在烘箱中干燥，充分研磨后转入马弗炉中，以5℃/min的升温速率升至400℃保持2h，即得Sm-TiO2-15复合纳米光催化剂。
实施例5
将0.44g二水合氯化钙溶解于15ml聚乙二醇-200及45ml无水乙醇的混合溶剂中，混合均匀，在不断搅拌下按钛：镱摩尔比为20：1加入0.0854g硝酸镱至上述混合溶液中搅拌均匀，随后缓慢加入1.32ml钛酸四丁酯，完全溶解后加入0.96g的氢氧化钠搅拌1h。将得到混合物转移到100ml高压反应釜中在180℃下反应15h，冷却后将所得产物分别用去离子水和无水乙醇洗涤三次，烘干研磨后取0.3g样品溶解于15ml乙二醇及45ml去离子水混合溶剂中，搅拌均匀后加入1.36g的EDTA-2Na，混合溶液搅拌均匀后转移到100ml高压反应釜中，在180℃烘箱中分别反应15h，鳌合反应结束后冷却至室温，分别用无水乙醇和去离子水真空抽滤洗涤，得到的样品在烘箱中干燥，充分研磨后转入马弗炉中，以5℃/min的升温速率升至400℃保持2h，即得Yb-TiO2-15复合纳米光催化剂。
实施例6
将0.44g二水合氯化钙溶解于15ml聚乙二醇-200及45ml无水乙醇的混合溶剂中，混合均匀，在不断搅拌下按钛：铥摩尔比为20：1加入0.0846g硝酸铥至上述混合溶液中搅拌均匀，随后缓慢加入1.32ml钛酸四丁酯，完全溶解后加入0.96g的氢氧化钠搅拌1h。将得到混合物转移到100ml高压反应釜中在180℃下反应15h，冷却后将所得产物分别用去离子水和无水乙醇洗涤三次，烘干研磨后取0.3g样品溶解于15ml乙二醇及45ml去离子水混合溶剂中，搅拌均匀后加入1.36g的EDTA-2Na，混合溶液搅拌均匀后转移到100ml高压反应釜中，在180℃烘箱中分别反应15h，鳌合反应结束后冷却至室温，分别用无水乙醇和去离子水真空抽滤洗涤，得到的样品在烘箱中干燥，充分研磨后转入马弗炉中，以5℃/min的升温速率升至400℃保持2h，即得Tm-TiO2-15复合纳米光催化剂。
按上述实施例1-6的方法分别制备得到纯TiO2和不同稀土元素掺杂的TiO2光催化剂、不同铜沉积量的T60S1复合光催化剂。图1为实施例1-6所制备的纯TiO2和不同稀土元素掺杂的TiO2光催化剂的X射线衍射图谱，通过图1XRD衍射图中可看到位于25.28°、37.80°、38.57°、48.05°、53.89°、55.06°、62.12°、70.31°和75.03°附近的衍射峰分别对应于锐钛矿型TiO2，33.1°附近的衍射峰归属于板钛矿Ti3O5相，XRD图谱中并没有发现明显的镧系金属的衍射峰，这可能掺杂比例过低造成的。放大位于25.28°的特征峰，由图可以看出(101)晶面的特征峰发生偏移，进一步证明镧系金属掺杂入晶格中。
实施例1和实施例6所制备的Tm-TiO2空心盒子的扫描电镜和透射电镜如图2、3所示。由图2、3可以看出，镧系金属掺杂的二氧化钛以及纯二氧化钛都形成了由颗粒聚集的空心正六面体盒子，透射电镜与高分辨透射电镜图更清楚地显示了样品的中空结构。
用所制备的不同稀土元素掺杂的TiO2空心盒子来催化降解抗蚜威、三唑酮、杀螟磷硫、溴氰菊酯，按照下述步骤进行：分别称取50mg不同稀土元素掺杂的TiO2空心盒子和为掺杂稀土元素的TiO2空心盒子放入250mL烧杯中构成六组平行试验，分别加入抗蚜威、三唑酮、杀螟磷硫及溴氰菊酯的混合溶液(均为20mg/L)，用250W金卤灯(上海亚明灯泡厂)作为光源，进行光催化降解反应。暗反应时间为30min，光照以后，每隔20min取一次样。在10000rpm条件下高速离心取上清液用0.22μm滤膜过滤，用液相色谱-质谱联用仪测其浓度变化。
由图4可见，在180min内实施例6制备的铥元素掺杂的TiO2空心盒子降解混合农药的效果最佳，四种农药几乎完全降解。所有样品对四类农药均有较好的降解效果，这可能是由于空心盒子结构具有较大的比表面积、而Tm-TiO2拥有最佳活性，是因为Tm掺杂后TiO2有更多的表面氧空位、较快的电子空穴传输速率和较强的光吸收能力。
Claims (6)
1.一种镧系金属掺杂TiO2中空纳米盒子催化剂的制备方法，其特征在于，包括以下步骤：
S1 将0.44g二水合氯化钙溶解于12～16mL聚乙二醇-200及40～50mL无水乙醇的混合溶剂中，混合均匀，获得混合溶液，在搅拌状态下加入镧系水合硝酸盐至上述混合溶液中搅拌均匀，随后加入钛酸四丁酯，完全溶解后加入0.9～1g的氢氧化钠搅拌1h，获得混合物；
S2 将S1得到混合物转移至100mL高压反应釜中，在180℃下反应12～16h冷却至室温后，将所得产物分别用去离子水和无水乙醇洗涤干净，烘干研磨，获得样品；
S3 取0.3gS2所得的样品溶解于12～16mL乙二醇及40～50mL去离子水混合溶剂中，搅拌均匀后加入1.2～1.4g的EDTA-2Na，搅拌均匀后转移到100mL高压反应釜中，在180℃烘箱中反应12～16h，鳌合反应结束后冷却至室温；
S4 分别用无水乙醇和去离子水真空抽滤洗涤，之后在烘箱中干燥，充分研磨后转入马弗炉中加热，即得镧系金属掺杂TiO2中空纳米盒子催化剂。
2.根据权利要求1所述的一种镧系金属掺杂TiO2中空纳米盒子催化剂的制备方法，其特征在于，所述S1中钛酸四丁酯、镧系水合硝酸盐的摩尔比为20：1。
3.根据权利要求1所述的一种镧系金属掺杂TiO2中空纳米盒子催化剂的制备方法，其特征在于，所述S3中乙二醇、去离子水的体积比为1:3。
4.根据权利要求1所述的一种镧系金属掺杂TiO2中空纳米盒子催化剂的制备方法，其特征在于，所述S4中转入马弗炉中加热以5℃/min的升温速率升至400℃后保持2h。
5.根据权利要求1-4任意一项一种镧系金属掺杂TiO2中空纳米盒子催化剂的制备方法制备的镧系金属掺杂TiO2中空纳米盒子催化剂，其特征在于，所述掺杂的金属为La、Ce、Sm、Yb、Tm中的至少一种。
6.根据权利要求1-4任意一项一种镧系金属掺杂TiO2中空纳米盒子催化剂的制备方法制备的镧系金属掺杂TiO2中空纳米盒子催化剂的应用，其特征在于，所属镧系金属掺杂TiO2中空纳米盒子催化剂应用于新烟碱类农药降解。
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