CN113351014A - 一种纳米复合甲醛分解材料 - Google Patents
一种纳米复合甲醛分解材料 Download PDFInfo
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- CN113351014A CN113351014A CN202110615641.8A CN202110615641A CN113351014A CN 113351014 A CN113351014 A CN 113351014A CN 202110615641 A CN202110615641 A CN 202110615641A CN 113351014 A CN113351014 A CN 113351014A
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 239000000463 material Substances 0.000 title claims abstract description 28
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 17
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 17
- 239000004113 Sepiolite Substances 0.000 claims abstract description 64
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 62
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 62
- 239000000843 powder Substances 0.000 claims abstract description 54
- 239000004575 stone Substances 0.000 claims abstract description 37
- 229940070527 tourmaline Drugs 0.000 claims abstract description 26
- 229910052613 tourmaline Inorganic materials 0.000 claims abstract description 26
- 239000011032 tourmaline Substances 0.000 claims abstract description 26
- 229940019931 silver phosphate Drugs 0.000 claims abstract description 22
- 229910000161 silver phosphate Inorganic materials 0.000 claims abstract description 22
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 20
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims abstract description 20
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 18
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 16
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 15
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 4
- 238000003756 stirring Methods 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- MXZROAOUCUVNHX-UHFFFAOYSA-N 2-Aminopropanol Chemical compound CCC(N)O MXZROAOUCUVNHX-UHFFFAOYSA-N 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- RQFQJYYMBWVMQG-IXDPLRRUSA-N chitotriose Chemical compound O[C@@H]1[C@@H](N)[C@H](O)O[C@H](CO)[C@H]1O[C@H]1[C@H](N)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)[C@@H](CO)O1 RQFQJYYMBWVMQG-IXDPLRRUSA-N 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 11
- 239000001488 sodium phosphate Substances 0.000 claims description 11
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 11
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 11
- 150000001413 amino acids Chemical class 0.000 claims description 10
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 10
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 10
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 239000004475 Arginine Substances 0.000 claims description 4
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004472 Lysine Substances 0.000 claims description 4
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 4
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 4
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 3
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 3
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 3
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 abstract description 20
- 239000004155 Chlorine dioxide Substances 0.000 abstract description 10
- 235000019398 chlorine dioxide Nutrition 0.000 abstract description 10
- 239000007787 solid Substances 0.000 abstract description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 7
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 abstract description 6
- ZCTXEAQXZGPWFG-UHFFFAOYSA-N imidurea Chemical compound O=C1NC(=O)N(CO)C1NC(=O)NCNC(=O)NC1C(=O)NC(=O)N1CO ZCTXEAQXZGPWFG-UHFFFAOYSA-N 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- 229910052709 silver Inorganic materials 0.000 abstract description 5
- 239000004332 silver Substances 0.000 abstract description 5
- 229910000166 zirconium phosphate Inorganic materials 0.000 abstract description 5
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 229940100530 zinc ricinoleate Drugs 0.000 abstract description 3
- GAWWVVGZMLGEIW-GNNYBVKZSA-L zinc ricinoleate Chemical compound [Zn+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GAWWVVGZMLGEIW-GNNYBVKZSA-L 0.000 abstract description 3
- 229920000881 Modified starch Polymers 0.000 abstract 1
- 230000005923 long-lasting effect Effects 0.000 abstract 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- -1 oxygen ions Chemical class 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 238000006683 Mannich reaction Methods 0.000 description 4
- 239000002262 Schiff base Substances 0.000 description 4
- 150000004753 Schiff bases Chemical class 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000008280 blood Substances 0.000 description 4
- 210000004369 blood Anatomy 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
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- 230000008929 regeneration Effects 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01D—SEPARATION
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
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- B01D53/34—Chemical or biological purification of waste gases
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- 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
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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Abstract
本发明公开一种纳米复合甲醛分解材料，包括以下质量份组分:氨基改性海泡石100份、2‑咪唑烷酮10～20份、咪唑烷基脲5～10份、固体二氧化氯0.5～1份、镧/铈掺杂纳米托玛琳粉15～30份、纳米硫化铜/磷酸银改性六环石10～20份、载银磷酸锆2～4份、蓖麻油酸锌5～10份、预糊化淀粉5～10份。本发明首次采用氨基改性海泡石、2‑咪唑烷酮、咪唑烷基脲、固体二氧化氯、镧/铈掺杂纳米托玛琳粉、纳米硫化铜/磷酸银改性六环石复配甲醛净化材料，五者协同作用，实现甲醛的固定化和长效持久降解。
Description
技术领域
本发明属于纳米材料领域，具体涉及一种纳米复合甲醛分解材料。
背景技术
甲醛，俗称蚁醛，是具有窒息性剌激性臭味的无色可燃气体，对人眼、鼻等有刺激作用。甲酸作为一种重要的化工原料，在木材、建材、橡胶、皮革、树脂、医药、纺织、轻工等行业有着广泛的应用，装修用的壁纸、木材、油漆、家具都能释放甲醛。甲醛能与人体的蛋白质反应生成氮亚甲基化合物，使蛋白质发生变性，是一类致癌物，当室内甲醛浓度达到0.1mg/m3时，就会有异味，使人产生不适感，达到30mg/m3时，就会致人立即死亡。
目前，甲醛的处理方法主要依赖于多孔材料的吸附性，虽能在一定程度上吸收甲醛气体，但是传统多孔吸附材料无法实现甲醛的分解，当吸附材料达到吸附饱和时，无法继续吸收甲醛，同时，再生难度高，净化成本高，且在较高温度条件下，还容易造成所吸附的甲醛的二次释放。因此，如何研制出可快速吸收甲醛且能持续高效分解甲醛的净化材料具有重要意义。
发明内容
针对现有技术的不足之处，本发明的目的在于提供一种纳米复合甲醛分解材料。
本发明的技术方案概述如下:
一种纳米复合甲醛分解材料，其特征在于，包括以下质量份组分:
所述氨基改性海泡石的制备方法为:
I:将海泡石研磨至300～500目，加入混合酸溶液中，控制固液比为0.5g/mL，搅拌处理10～15min，过滤、洗涤、干燥后，得海泡石粉末；
II:将海泡石粉末置于马弗炉中，300～500℃煅烧4～6h，得预处理后海泡石粉末；
III:将壳寡糖、碱性氨基酸、氨基丙醇、四亚乙基五胺溶解于去离子水中，再加入预处理后海泡石粉末，于0.5～1MPa压力下，加压浸渍吸附1～2h后，过滤，60～80℃脱水干燥0.5～1h，即得所述氨基改性海泡石。
优选的是，所述壳寡糖、碱性氨基酸、氨基丙醇、四亚乙基五胺、预处理后海泡石粉末、去离子水的质量比为(0.2～0.3):(0.1～0.2):(0.1～0.2):(0.05～0.1):1:3。
优选的是，所述镧/铈掺杂纳米托玛琳粉的制备方法为:向无水乙醇中加入六水硝酸镧、六水硝酸铈，搅拌溶解后，加入纳米托玛琳粉，超声分散后，于80～100℃旋转蒸发乙醇，即得所述镧/铈掺杂纳米托玛琳粉。
优选的是，所述六水硝酸镧、六水硝酸铈、纳米托玛琳粉、无水乙醇的质量比为(0.05～0.1):(0.03～0.05):1:5。
优选的是，所述纳米硫化铜/磷酸银改性六环石的制备方法为:将六环石研磨至300～500目，加入0.01mol/L磷酸钠溶液中，再加入聚乙二醇，搅拌溶解后，再滴加0.03mol/L硝酸银溶液，搅拌反应0.5～1h，离心、洗涤后，再加入0.01mol/L硫化钠溶液中，滴加0.01mol/L硝酸铜溶液，搅拌反应0.5～1h，离心、洗涤、干燥后，即得所述纳米硫化铜/磷酸银改性六环石。
优选的是，所述六环石、磷酸钠溶液、聚乙二醇、硝酸银溶液、硫化钠溶液、硝酸铜溶液的用量比为1g:(3～5)mL:(0.05～0.1)g:(3～5)mL:(5～10)mL:(5～10)mL。
优选的是，所述混合酸溶液由0.1mol/L HCl溶液与0.05mol/L HF溶液按照1:(0.1～0.2)的体积比混合而成。
优选的是，所述碱性氨基酸为精氨酸、赖氨酸、组氨酸中的一种或多种。
本发明的有益效果:
1、本发明首次采用氨基改性海泡石、2-咪唑烷酮、咪唑烷基脲、固体二氧化氯、镧/铈掺杂纳米托玛琳粉、纳米硫化铜/磷酸银改性六环石复配甲醛净化材料，五者协同作用，实现甲醛的固定化和长效持久降解。氨基改性海泡石先经酸洗、煅烧处理，提高海泡石的比表面积、孔隙率，进而提高净化材料对甲醛的吸附性能，再利用壳寡糖、碱性氨基酸、氨基丙醇进行改性，使海泡石表面和孔道结构中富集大量-NH2，-NH2与HCHO发生席夫碱反应或曼尼希反应，生成常温下稳定的曼氏碱、席夫碱配合物，进而实现甲醛的固定化，达到清除甲醛的作用，利用2-咪唑烷酮、咪唑烷基脲中的-NH-与HCHO发生曼尼希反应，镧/铈掺杂纳米托玛琳粉释放大量负氧离子，负氧离子与固体二氧化氯可将甲醛彻底降解为CO2和H2O，同时，负氧离子能提高血液中的含氧量，有利于血氧输送、吸收和利用，具有促进人体新陈代谢，提高人体免疫能力，固体二氧化氯分解甲醛反应方程式为：4ClO2+5HCHO＝5CO2+4HCl+3H2O，纳米硫化铜/磷酸银改性六环石兼具可见光催化和释放负离子功能，在太阳光辐射下，能快速将甲醛氧化降解成CO2和H2O。
2、本发明利用载银磷酸锆抑菌杀菌，同时，二氧化氯能高效氧化细胞内含巯基的酶、硫化物或氮化物，使氨基酸氧化分解，抑制蛋白质的合成，二者协同抗菌。
3、本发明蓖麻油酸锌对H2S、NH3、有机硫化物、TVOC等具有明显去除效果，清除室内臭味，保持清新空气。
4、本发明以六环石为载体，形成纳米硫化铜/磷酸银异质结光催化剂，实现光生电子和空穴地高效分离，同时，扩大光谱响应范围，提高太阳光利用率，进而显著提高纳米硫化铜/磷酸银改性六环石对甲醛的光降解性能。
具体实施方式
下面结合实施例对本发明做进一步的详细说明，以令本领域技术人员参照说明书文字能够据以实施。
实施例1
一种纳米复合甲醛分解材料，其特征在于，包括以下质量份组分:
所述氨基改性海泡石的制备方法为:
I:将海泡石研磨至300目，加入混合酸溶液中，控制固液比为0.5g/mL，搅拌处理10min，过滤、洗涤、干燥后，得海泡石粉末；所述混合酸溶液由0.1mol/LHCl溶液与0.05mol/L HF溶液按照1:0.1的体积比混合而成；
II:将海泡石粉末置于马弗炉中，300℃煅烧4h，得预处理后海泡石粉末；
III:将壳寡糖、精氨酸、氨基丙醇、四亚乙基五胺溶解于去离子水中，再加入预处理后海泡石粉末，控制壳寡糖、精氨酸、氨基丙醇、四亚乙基五胺、预处理后海泡石粉末、去离子水的质量比为0.2:0.1:0.1:0.05:1:3，于0.5MPa压力下，加压浸渍吸附1h后，过滤，60℃脱水干燥0.5h，即得所述氨基改性海泡石。
所述镧/铈掺杂纳米托玛琳粉的制备方法为:向无水乙醇中加入六水硝酸镧、六水硝酸铈，搅拌溶解后，加入纳米托玛琳粉，控制六水硝酸镧、六水硝酸铈、纳米托玛琳粉、无水乙醇的质量比为0.05:0.03:1:5，超声分散后，于80℃旋转蒸发乙醇，即得所述镧/铈掺杂纳米托玛琳粉。
所述纳米硫化铜/磷酸银改性六环石的制备方法为:将六环石研磨至300目，加入0.01mol/L磷酸钠溶液中，再加入聚乙二醇，搅拌溶解后，再滴加0.03mol/L硝酸银溶液，搅拌反应0.5h，离心、洗涤后，再加入0.01mol/L硫化钠溶液中，滴加0.01mol/L硝酸铜溶液，搅拌反应0.5h，离心、洗涤、干燥后，即得所述纳米硫化铜/磷酸银改性六环石；所述六环石、磷酸钠溶液、聚乙二醇、硝酸银溶液、硫化钠溶液、硝酸铜溶液的用量比为1g:3mL:0.05g:3mL:5mL:5mL。
实施例2
一种纳米复合甲醛分解材料，其特征在于，包括以下质量份组分:
所述氨基改性海泡石的制备方法为:
I:将海泡石研磨至300～500目，加入混合酸溶液中，控制固液比为0.5g/mL，搅拌处理15min，过滤、洗涤、干燥后，得海泡石粉末；所述混合酸溶液由0.1mol/LHCl溶液与0.05mol/L HF溶液按照1:0.15的体积比混合而成；
II:将海泡石粉末置于马弗炉中，400℃煅烧5h，得预处理后海泡石粉末；
III:将壳寡糖、赖氨酸、氨基丙醇、四亚乙基五胺溶解于去离子水中，再加入预处理后海泡石粉末，控制壳寡糖、赖氨酸、氨基丙醇、四亚乙基五胺、预处理后海泡石粉末、去离子水的质量比为0.25:0.15:0.15:0.075:1:3，于0.75MPa压力下，加压浸渍吸附1.5h后，过滤，70℃脱水干燥1h，即得所述氨基改性海泡石。
所述镧/铈掺杂纳米托玛琳粉的制备方法为:向无水乙醇中加入六水硝酸镧、六水硝酸铈，搅拌溶解后，加入纳米托玛琳粉，控制六水硝酸镧、六水硝酸铈、纳米托玛琳粉、无水乙醇的质量比为0.075:0.04:1:5，超声分散后，于90℃旋转蒸发乙醇，即得所述镧/铈掺杂纳米托玛琳粉。
所述纳米硫化铜/磷酸银改性六环石的制备方法为:将六环石研磨至400目，加入0.01mol/L磷酸钠溶液中，再加入聚乙二醇，搅拌溶解后，再滴加0.03mol/L硝酸银溶液，搅拌反应1h，离心、洗涤后，再加入0.01mol/L硫化钠溶液中，滴加0.01mol/L硝酸铜溶液，搅拌反应1h，离心、洗涤、干燥后，即得所述纳米硫化铜/磷酸银改性六环石；所述六环石、磷酸钠溶液、聚乙二醇、硝酸银溶液、硫化钠溶液、硝酸铜溶液的用量比为1g:4mL:0.075g:4mL:7.5mL:7.5mL。
实施例3
一种纳米复合甲醛分解材料，其特征在于，包括以下质量份组分:
所述氨基改性海泡石的制备方法为:
I:将海泡石研磨至300～500目，加入混合酸溶液中，控制固液比为0.5g/mL，搅拌处理15min，过滤、洗涤、干燥后，得海泡石粉末；所述混合酸溶液由0.1mol/LHCl溶液与0.05mol/L HF溶液按照1:0.2的体积比混合而成；
II:将海泡石粉末置于马弗炉中，500℃煅烧6h，得预处理后海泡石粉末；
III:将壳寡糖、组氨酸、氨基丙醇、四亚乙基五胺溶解于去离子水中，再加入预处理后海泡石粉末，控制壳寡糖、组氨酸、氨基丙醇、四亚乙基五胺、预处理后海泡石粉末、去离子水的质量比为0.3:0.2:0.2:0.1:1:3，于1MPa压力下，加压浸渍吸附2h后，过滤，80℃脱水干燥1h，即得所述氨基改性海泡石。
所述镧/铈掺杂纳米托玛琳粉的制备方法为:向无水乙醇中加入六水硝酸镧、六水硝酸铈，搅拌溶解后，加入纳米托玛琳粉，控制六水硝酸镧、六水硝酸铈、纳米托玛琳粉、无水乙醇的质量比为0.1:0.05:1:5，超声分散后，于100℃旋转蒸发乙醇，即得所述镧/铈掺杂纳米托玛琳粉。
所述纳米硫化铜/磷酸银改性六环石的制备方法为:将六环石研磨至500目，加入0.01mol/L磷酸钠溶液中，再加入聚乙二醇，搅拌溶解后，再滴加0.03mol/L硝酸银溶液，搅拌反应1h，离心、洗涤后，再加入0.01mol/L硫化钠溶液中，滴加0.01mol/L硝酸铜溶液，搅拌反应1h，离心、洗涤、干燥后，即得所述纳米硫化铜/磷酸银改性六环石；所述六环石、磷酸钠溶液、聚乙二醇、硝酸银溶液、硫化钠溶液、硝酸铜溶液的用量比为1g:5mL:0.1g:5mL:10mL:10mL。
对比例1同实施例1，区别在于：将实施例1中所选用的氨基改性海泡石替换为酸洗海泡石，所述酸洗海泡石的制备方法为：I:将海泡石研磨至300目，加入混合酸溶液中，控制固液比为0.5g/mL，搅拌处理10min，过滤、洗涤、干燥后，得海泡石粉末；所述混合酸溶液由0.1mol/L HCl溶液与0.05mol/L HF溶液按照1:0.1的体积比混合而成；
II:将海泡石粉末置于马弗炉中，300℃煅烧4h，得酸洗海泡石。
对比例2同实施例1，区别在于：将实施例1中所用的纳米硫化铜/磷酸银改性六环石替换为300目六环石粉，即不采用纳米硫化铜/磷酸银进行沉淀改性。
对比例3同实施例1，区别在于：将实施例1中所用的纳米硫化铜/磷酸银改性六环石替换为纳米磷酸银改性六环石，其制备方法为：将六环石研磨至300目，加入0.01mol/L磷酸钠溶液中，再加入聚乙二醇，搅拌溶解后，再滴加0.03mol/L硝酸银溶液，搅拌反应0.5h，离心、洗涤、干燥后，即得所述纳米磷酸银改性六环石。
甲醛降解试验：
将300mg实施例1/实施例2/实施例3/对比例1/对比例2//对比例3填充在2L圆柱型反应器内，再打开500W氙灯灯源，并用滤光片使420nm以上波长的可见光通过，照射到反应体系内，反应器内甲醛初始浓度为200ppm，设定反应器内气体循环流量为100ml/min，反应60min，用甲醛分析仪，测定反应后甲醛浓度C，根据公式：100％×[(200-C)/200]计算甲醛降解率。
下表列出实施例1-3及对比例1-3对甲醛降解率试验结果：
| 实施例1 | 实施例2 | 实施例3 | 对比例1 | 对比例2 | 对比例3 |
| 92.7 | 96.4 | 99.3 | 63.1 | 79.2 | 68.5 |
实施例1～3首次采用氨基改性海泡石、2-咪唑烷酮、咪唑烷基脲、固体二氧化氯、镧/铈掺杂纳米托玛琳粉、纳米硫化铜/磷酸银改性六环石复配甲醛净化材料，五者协同作用，实现甲醛的固定化和长效持久降解。氨基改性海泡石先经酸洗、煅烧处理，提高海泡石的比表面积、孔隙率，进而提高净化材料对甲醛的吸附性能，再利用氨基纤维素、碱性氨基酸、氨基丁醇进行改性，使海泡石表面和孔道结构中富集大量-NH2，-NH2与HCHO发生席夫碱反应或曼尼希反应，生成常温下稳定的曼氏碱、席夫碱配合物，进而实现甲醛的固定化，达到清除甲醛的作用，利用2-咪唑烷酮、咪唑烷基脲中的-NH-与HCHO发生曼尼希反应，镧/铈掺杂纳米托玛琳粉释放大量负氧离子，负氧离子与固体二氧化氯可将甲醛彻底降解为CO2和H2O，同时，负氧离子能提高血液中的含氧量，有利于血氧输送、吸收和利用，具有促进人体新陈代谢，提高人体免疫能力，固体二氧化氯分解甲醛反应方程式为：4ClO2+5HCHO＝5CO2+4HCl+3H2O，纳米硫化铜/磷酸银改性六环石兼具可见光催化和释放负离子功能，在太阳光辐射下，能快速将甲醛氧化降解成CO2和H2O。
实施例1～3利用载银磷酸锆抑菌杀菌，同时，二氧化氯能高效氧化细胞内含巯基的酶、硫化物或氮化物，使氨基酸氧化分解，抑制蛋白质的合成，二者协同抗菌。
实施例1～3蓖麻油酸锌对H2S、NH3、有机硫化物、TVOC等具有明显去除效果，清除室内臭味，保持清新空气。
实施例1～3以六环石为载体，形成纳米硫化铜/磷酸银异质结光催化剂，实现光生电子和空穴地高效分离，同时，扩大光谱响应范围，提高太阳光利用率，进而显著提高纳米硫化铜/磷酸银改性六环石对甲醛的光降解性能。
尽管本发明的实施方案已公开如上，但其并不仅仅限于说明书和实施方式中所列运用，它完全可以被适用于各种适合本发明的领域，对于熟悉本领域的人员而言，可容易地实现另外的修改，因此在不背离权利要求及等同范围所限定的一般概念下，本发明并不限于特定的细节。
Claims (8)
1.一种纳米复合甲醛分解材料，其特征在于，包括以下质量份组分:
所述氨基改性海泡石的制备方法为:
I:将海泡石研磨至300～500目，加入混合酸溶液中，控制固液比为0.5g/mL，搅拌处理10～15min，过滤、洗涤、干燥后，得海泡石粉末；
II:将海泡石粉末置于马弗炉中，300～500℃煅烧4～6h，得预处理后海泡石粉末；
III:将壳寡糖、碱性氨基酸、氨基丙醇溶解于去离子水中，再加入预处理后海泡石粉末，于0.5～1MPa压力下，加压浸渍吸附1～2h后，过滤，60～80℃脱水干燥0.5～1h，即得所述氨基改性海泡石。
2.根据权利要求1所述一种纳米复合甲醛分解材料，其特征在于，所述壳寡糖、碱性氨基酸、氨基丙醇、四亚乙基五胺、预处理后海泡石粉末、去离子水的质量比为(0.2～0.3):(0.1～0.2):(0.1～0.2):(0.05～0.1):1:3。
3.根据权利要求1所述一种纳米复合甲醛分解材料，其特征在于，所述镧/铈掺杂纳米托玛琳粉的制备方法为:向无水乙醇中加入六水硝酸镧、六水硝酸铈，搅拌溶解后，加入纳米托玛琳粉，超声分散后，于80～100℃旋转蒸发乙醇，即得所述镧/铈掺杂纳米托玛琳粉。
4.根据权利要求3所述一种纳米复合甲醛分解材料，其特征在于，所述六水硝酸镧、六水硝酸铈、纳米托玛琳粉、无水乙醇的质量比为(0.05～0.1):(0.03～0.05):1:5。
5.根据权利要求1所述一种纳米复合甲醛分解材料，其特征在于，所述纳米硫化铜/磷酸银改性六环石的制备方法为:将六环石研磨至300～500目，加入0.01mol/L磷酸钠溶液中，再加入聚乙二醇，搅拌溶解后，再滴加0.03mol/L硝酸银溶液，搅拌反应0.5～1h，离心、洗涤后，再加入0.01mol/L硫化钠溶液中，滴加0.01mol/L硝酸铜溶液，搅拌反应0.5～1h，离心、洗涤、干燥后，即得所述纳米硫化铜/磷酸银改性六环石。
6.根据权利要求5所述一种纳米复合甲醛分解材料，其特征在于，所述六环石、磷酸钠溶液、聚乙二醇、硝酸银溶液、硫化钠溶液、硝酸铜溶液的用量比为1g:(3～5)mL:(0.05～0.1)g:(3～5)mL:(5～10)mL:(5～10)mL。
7.根据权利要求1所述一种纳米复合甲醛分解材料，其特征在于，所述混合酸溶液由0.1mol/L HCl溶液与0.05mol/L HF溶液按照1:(0.1～0.2)的体积比混合而成。
8.根据权利要求1所述一种纳米复合甲醛分解材料，其特征在于，所述碱性氨基酸为精氨酸、赖氨酸、组氨酸中的一种或多种。
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