CN114423523A - 光催化陶瓷 - Google Patents
光催化陶瓷 Download PDFInfo
- Publication number
- CN114423523A CN114423523A CN202080061532.XA CN202080061532A CN114423523A CN 114423523 A CN114423523 A CN 114423523A CN 202080061532 A CN202080061532 A CN 202080061532A CN 114423523 A CN114423523 A CN 114423523A
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- CN
- China
- Prior art keywords
- ceramic
- photocatalytic
- functionalized
- amorphous
- biomimetic
- Prior art date
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- Pending
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- 239000000919 ceramic Substances 0.000 title claims abstract description 80
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 53
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 239000011265 semifinished product Substances 0.000 claims abstract description 25
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 20
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 16
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 16
- 239000002977 biomimetic material Substances 0.000 claims abstract description 15
- 239000005300 metallic glass Substances 0.000 claims abstract description 13
- 239000012620 biological material Substances 0.000 claims abstract description 12
- 230000003592 biomimetic effect Effects 0.000 claims abstract description 10
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 9
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 60
- 239000010936 titanium Substances 0.000 claims description 54
- 239000011135 tin Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 32
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 27
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 27
- 239000000725 suspension Substances 0.000 claims description 22
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 19
- 229910021645 metal ion Inorganic materials 0.000 claims description 18
- 229910052718 tin Inorganic materials 0.000 claims description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
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- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000007306 functionalization reaction Methods 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- XAAHAAMILDNBPS-UHFFFAOYSA-L calcium hydrogenphosphate dihydrate Chemical compound O.O.[Ca+2].OP([O-])([O-])=O XAAHAAMILDNBPS-UHFFFAOYSA-L 0.000 claims description 7
- 239000011941 photocatalyst Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 7
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 7
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- -1 monetite Chemical compound 0.000 claims description 3
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- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910009256 Sn(CH3SO3)2 Inorganic materials 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 230000000845 anti-microbial effect Effects 0.000 claims description 2
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
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- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001848 post-transition metal Inorganic materials 0.000 claims description 2
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- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims 1
- 239000004599 antimicrobial Substances 0.000 claims 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims 1
- 239000001110 calcium chloride Substances 0.000 claims 1
- 229910001628 calcium chloride Inorganic materials 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 claims 1
- 238000010304 firing Methods 0.000 abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 4
- 150000004706 metal oxides Chemical class 0.000 abstract description 4
- 229910052976 metal sulfide Inorganic materials 0.000 abstract description 4
- 150000003568 thioethers Chemical class 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- 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
- B01J27/14—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
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
- A61L2/08—Radiation
- A61L2/088—Radiation using a photocatalyst or photosensitiser
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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Abstract
本发明涉及用于生产抗菌光催化陶瓷的方法,其包括:‑制备可用的至少一种非晶态金属;‑制备可用的基于钙磷酸盐的仿生材料或生物材料;‑用所述至少一种非晶态金属将基于钙磷酸盐的所述仿生材料或所述生物材料功能化,从而获得功能化且取向的复合材料;‑将所述功能化的复合材料添加至陶瓷混合物,和/或在陶瓷半成品上施加所述功能化的复合材料,其中陶瓷半成品意指烘烤之前的陶瓷材料;‑在陶瓷半成品上施加所述功能化的复合材料;‑在600和1400℃之间、优选在900和1300℃之间的温度下烘烤持续从20至500分钟变化的时间,从而获得抗菌光催化陶瓷。本发明还涉及光催化陶瓷材料和包含光催化陶瓷材料的砖瓦、卫生器具和餐具,该光催化陶瓷材料包含具有纳米结构化的分级结构的仿生材料,所述纳米结构化的分级结构有宏观腔和微观腔,在所述腔内包括至少一种光催化材料,所述光催化材料选自处于具有类金红石结构的晶态形式的金属氧化物和/或硫化物。
Description
现有技术
陶瓷是建筑物中使用最多的材料之一,并且随着日益提高的兴趣,陶瓷在配件领域中常见到,在厨房和浴室配件区中用作覆盖物和/或用作制造硬质零件用的构造元件(例如柜台面和/或后挡板)。用途范围从住宅区到招待性行业(hospitality)和研究实验室。
使用具有抗微生物性质的陶瓷材料具有明显优势。光催化是通过光催化剂产生强氧化过程的自然现象,其将有机和无机污染物分解,从而将它们转化为无害物质。二氧化钛TiO2从在光催化中研究最多的材料当中脱颖而出。TiO2结合长期稳定性和对生物圈的低毒性与良好光催化活性。近年来对于大气和水的以下大范围污染物研究了TiO2的光催化性质:醇类、卤化物、芳香烃类。进行的研究给出了对于有机酸、染料、NOx等的有希望的结果。出于这些原因,TiO2已经广泛用于表面处理中。
TiO2的这些性质已应用于在水中和在空气中以及在表面上特别是在医疗/医院环境中的细菌和有害有机材料的去除。TiO2的活性受各种因素的影响,例如晶体结构、表面、纳米颗粒的尺寸分布、孔隙率、TiO2表面上的羟基基团的数量和密度。
事实上TiO2以非晶态形式或以晶态形式存在,并且非晶态形式是无光催化活性的。已知TiO2的三种天然晶态形式,称作锐钛矿、金红石和板钛矿。锐钛矿和金红石具有四方结构,而板钛矿的结构是正交的。板钛矿是较不常见的形式。锐钛矿和金红石是光催化活性的,而板钛矿从未被测试过光催化活性。与金红石相比,纯的锐钛矿作为光催化剂更有活性,可能是因为它在导带的边缘具有更高的负电势(这意味着光生电子的更高势能)和在其表面上更大数量的羟基基团。
Luttrell T.等人,Scientific Reports 4,Article Number 4043,2014描述了金红石和锐钛矿的较高或较低的光催化活性可能取决于它们所沉积表面的性质和取决于在表面上所沉积涂层的厚度。例如,使用相同的表面条件,如果涂层厚于5nm,则锐钛矿达到其最大活性,而对于金红石而言2.5nm的涂层是足够的。可通过适当掺杂TiO2来提高这种活性。近年来,科学文献已富有对用金属氧化物掺杂TiO2的详细研究。
在300-500℃范围内煅烧时,观察到纯的锐钛矿形成。随着温度提高,观察到晶体的尺寸提高。在500-700℃之间煅烧时,获得混合的锐钛矿-金红石。
一些研究小组(Jung W.Y.等人,Synthesis of Ti-containing SBA-15materialsand studies on their photocatalytic decomposition of orange II.Catal.Today,131:437-443,2008;Lihitkar N.B.等人,Titania nanoparticles synthesis inmesoporous molecular sieve MCM-41.J.Colloid Interface Sci.,314:310-316,2007;Ikeda S.等人,Structural effects of titanium(IV)oxide encapsulated in a hollowsilica shell on photocatalytic activity for gas-phase decomposition oforganics.Appl.Cat.A:General,369:113-118,2009)将他们的注意力集中在通过提高TiO2的表面积,由此提高吸附在其表面上的分子数并促进电荷转移过程从而提高TiO2的光活性的可能性。
在另一种材料上引入光催化剂导致实用性质的优势。事实上,固定在载体上抑制或减缓颗粒的烧结,这是表面积降低的原因。
用于提高TiO2活性的另外的方法涉及作用于半导体的电子能级的可能性,降低带隙的能量从而能够使用比可见光更低频率的光将电子从价带(VB)提升到导带(CB)(ParidaK.M.,Naik B.Synthesis of mesoporous TiO2-xNx spheres by template freehomogeneous co-precipitation method and their photo-catalytic activity undervisible light illumination.J.Colloid Interface Sci.,333:269-276,2009;Irie H.等人,Nitrogen-Concentration Dependence on Photocatalytic Activity of TiO2-xNxPowders.J.Phys.Chem.B,107:5483-5486,2003;Asahi R.等人,Visible-lightphotocatalysis in nitrogen-doped titanium oxides.Science,293.269-271,2001)。这种方法设想通过掺杂来改性材料并且由在合成步骤中引入能够调节其电子性质的元素的合适前体组成。
从电子角度来看,TiO2是n-型半导体;锐钛矿的Eg值等于3.2eV,金红石的Eg值为3.0eV。从这些值,我们由等式(1)发现:
Eg=hν=hc/λ=1240/λ(1)
锐钛矿被具有波长λ≤388nm即来自电磁波谱的UVA部分的光“活化”,而金红石具有λ≤413nm,因此具有在可见区域中的光(PAR,400-700nm)。在等式(1)中,h表示普朗克常数,v是入射辐射的频率且c是光在真空中的速度;乘积hc(常数)以[eV×nm]为单位表示且波长λ以nm为单位。
WO2010146410A1描述在900和1250℃之间的温度下烘烤陶瓷基底并且然后在烘烤之后使用分散在水中的微米晶态TiO2以获得表面层,在其下沉积胶黏剂层。随后在600℃下热处理允许胶黏剂软化但不允许锐钛矿转化为金红石,其被认为是不充分光活性的。
EP1304366B2描述在通常为玻璃状的表面上沉积非晶态钛层。在525℃的最大温度下随后烘烤材料将非晶态钛转化为锐钛矿。
SnO2在光催化中起到的作用有限,其带隙即价带和导带之间的能隙需要对应于在太阳辐射中表现不佳的波长(326nm)的能量(3.8eV),这使得用太阳辐射或人工白光的光催化过程无效。
仿生学是多学科科学,其中使用生物方法设计新的“智能”材料或结构。例如,自然提供软和硬的材料,其特殊的功能性质取决于在宏观和纳米尺度水平构成它们的基础分子单元的分级组织。
强烈地认识到需要具有高抗菌活性的陶瓷材料,其可使用经济上可持续的生产方法获得。
发明内容
在本发明中,制备“生物启发的”陶瓷表面,其由具有模仿骨结构的分级结构、具有微观腔和宏观腔,并具有微米尺寸、纳米结构和生物相容性的新材料形成,其中在高温下在适合于制备具有尺寸、形态、结构和取向的晶体从而使其光催化性质特别有利的无机载体上具有金红石类型结构的至少一种金属的氧化物或硫化物结晶。
定义
在本文中,术语“陶瓷”或“陶瓷材料”或“陶瓷产品”意指由其组成的材料和成品。在成品中,本文强调涂覆和覆盖材料例如砖和屋顶瓦、卫生器具和餐具,因为这是本发明的目的特别关注的。
在本文中,术语“取向的功能化复合材料”或“复合材料”意指仿生材料,其包含以有序方式即相对于基材采用规则晶体学排列而排列的晶态类金红石形式的金属,其中基材意指所述仿生材料(Brinker C.J.1998Current Opinion in Colloid&InterfaceScience.3:166-173)。
在本文中,术语“陶瓷半成品”意指在模制和任选的干燥步骤之后的陶瓷材料,所述步骤典型地在烘烤过程之前。
术语“涂覆的陶瓷半成品”意指如以上提到的陶瓷材料,在其上施加包含根据本发明的取向的功能化复合材料的混合物。
在本文中,术语“陶瓷混合物”意指原材料的混合物,其在模制时将构成陶瓷半成品并因此构成陶瓷制品。
术语“富化(enriched)的陶瓷混合物”意指包含根据本发明的取向的功能化复合材料的陶瓷混合物。
附图描述
图1:nHA的X-射线衍射谱图。
图2:根据本发明的表面功能化方法的实施方案的示意图。点表示至少一种非晶态金属,并且菱形表示类金红石晶态形式的所述至少一种金属的氧化物和/或硫化物。黑条是陶瓷基材,并且线代表生物材料或仿生材料。
图3:(A)根据本发明第一实施方案Ti形式的光催化活性陶瓷表面的X-射线衍射谱图。(B)根据本发明Ti形式的光催化活性陶瓷表面的使用EDS光谱法(能量色散X-射线光谱法)获得的实例图像。照片分别显示P、Ca和Ti原子的表面定位。
图4:根据本发明根据第二实施方案Sn形式的光催化活性陶瓷表面的X-射线衍射谱图。突出锡石(casserite)(A)和钙长石(B)的典型峰。
图5:根据Ti形式实施方案的光催化活性陶瓷表面通过扫描电子显微镜(SEM)的检查。(A)羟基磷灰石微晶;(B)突出纳米结构化的分级结构的照片;(C)EDS微观分析谱图。
图6:根据Sn实施方案的光催化活性陶瓷表面的扫描电子显微镜(SEM)分析。(A)羟基磷灰石微晶;(B)EDS微量分析谱图。
图7:根据Ti实施方案的光催化陶瓷材料(a)或包含锐钛矿的商业光催化材料(b)在12小时(图片A)和在48小时(图片B)的光催化活性的对比测试。曲线(c)涉及在无光催化表面上获得的结果。
图8:(A)在实验7中照射样品所用的Philips PL-S 9W/2P BLB灯的发射谱;(B)在实验7中照射样品所用的6500K LED照明系统的发射谱;在包括如下的陶瓷砖上光催化测试期间用UV照射的NO、NO2和NOx浓度分布:(C)包括SnO2;(D)1:1包含金红石形式的TiO2和SnO2;(E)包含TiO2;在包括如下的陶瓷砖上光催化测试期间用可见光照射的NO、NO2和NOx浓度分布:(F)包括SnO2;(G)1:1包含金红石形式的TiO2和SnO2;(H)包含TiO2。
图9:光催化活性,罗丹明测试(A)吸光度曲线;(B)随时间的吸光度。
本发明首先涉及用于生产抗菌光催化陶瓷的方法,其包括:
—制备可用的至少一种非晶态金属;
—制备可用的基于钙磷酸盐的仿生材料和/或生物材料;
—用所述至少一种非晶态金属将基于钙磷酸盐的所述仿生材料和/或所述生物材料功能化,从而获得功能化且取向的复合材料;
—将所述功能化的复合材料添加至陶瓷混合物,和/或在陶瓷半成品上施加所述功能化的复合材料,其中陶瓷半成品意指烘烤之前的陶瓷材料;
—在600和1400℃之间、优选在900和1300℃之间的温度下烘烤持续从20至500分钟变化的时间,从而获得抗菌光催化陶瓷。
在一种实施方案中,所述至少一种非晶态形式的金属选自过渡金属(d区元素)和后过渡金属(p区元素)。
在一种实施方案中,所述至少一种金属选自包含以下的组:钛、锡、锌、锆、镉、钨。
在一种实施方案中,所述至少一种金属选自包含以下的组:硫酸氧钛(IV)、四氯化钛、四异丙氧基钛、异丙氧基钛、氯氧化钛、SnCl2、SnCl4、Sn(NO3)2、SnSO4、Sn(CH3SO3)2、WO3。
在一种实施方案中,Ti形式,所述方法包括制备可用的非晶态的钛,从而获得包含金红石形式TiO2的抗菌光催化陶瓷。
在一实施方案中,Sn形式,所述方法包括制备可用的非晶态的锡,从而获得包含类金红石晶态形式SnO2的抗菌光催化陶瓷。
在一实施方案中,Sn/Ti形式,所述方法包括制备可用的锡和非晶态的钛,从而获得包含类金红石晶态形式SnO2和金红石形式TiO2的抗菌光催化陶瓷。
在另一实施方案中,所述光催化陶瓷包含ZnO、ZnS、ZrO2、CdS和/或WO3。
所述材料(合成的(仿生的)或天然来源(生物材料)的)优选选自包含以下的组:透钙磷石、三斜磷钙石、羟基磷灰石(HA)、(β/α)磷酸三钙(TCP)。所述材料在表面上缺少钙。
在一种优选实施方案中,所述材料是纳米晶羟基磷灰石(nHA)。在7和14之间的pH、优选在pH 11下通过在剧烈搅拌下用磷酸逐滴中和氢氧化钙或醋酸钙或氯化钙或硝酸钙的悬浮液2-12小时从而有利地获得所述羟基磷灰石。该合成设想在表面Ca/P之间在1.55和1.70之间、优选1.64的摩尔比。
图1显示如此获得的nHA的衍射谱图,其显示nHA为具有羟基磷灰石的衍射极大值特性的晶态材料。所述nHA在表面处暴露正电荷和负电荷两者,这使它特别具有反应性。这表明所述nHA能够结合大量的至少一种非晶态金属并且能够粘合至陶瓷半成品的组分。
在所述功能化之后,所得的复合材料是功能化且取向的复合材料,即特征在于规则晶体学排列的材料。所述仿生材料或生物材料事实上由PO4 3-四面体结构组成,其包括在水平平面上的两个氧原子。本发明的作者出乎预料地显示所述至少一种非晶态金属结合在所述水平平面上排列的氧,在暴露于高于600℃、优选高于900℃的温度之后,形成类金红石晶体,其在有序的方向上生长,这由所述至少一种非晶态金属在所述平面上的所述沉积确定。
在一种实施方案(Ti形式)中,通过将所述非晶态Ti逐滴添加至在酸水解的情况(pH 1-6)下处于透钙磷石和/或三斜磷钙石形式或在碱性水解的情况(pH 7-14)下处于nHA或(β/α)TCP形式的钙磷酸盐的溶液来进行所述功能化。优选地,以相对于水解溶液的体积的10-30重量%、优选15%的量逐滴添加所述非晶态Ti,并且所述逐滴添加在剧烈搅拌下发生2-12小时。
在一种实施方案中,使用掺杂的钛进行所述功能化,并且在具有选自以下的一种或多种金属离子的悬浮液中逐滴添加所述非晶态Ti:Cu、Zn、Ag、Sr、Al、Sb、W、Mn、Sn、V、Cr、Zr、Mo、Pd,优选溶剂化的。在一种实施方案中,所述金属离子用10-30%的异丙醇或作为替代的乙醇溶剂化。
在一种实施方案中,存在至少两种金属离子。优选地,所述两种金属离子彼此为1/1比率。
在一种实施方案中,所述悬浮液包含10-30%(w/v)的所述非晶态Ti和0.1-0.5%(w/v)的所述一种或多种溶剂化的金属离子。
在一种实施方案(Sn形式)中,通过获得与包含nHA的悬浮液混合的所述非晶态锡的碱性水性悬浮液首先发生所述用非晶态锡功能化。
在一种实施方案中,使用掺杂的锡发生所述功能化,并且在具有选自以下的一种或多种金属离子的悬浮液中滴入所述非晶态锡:Cu、Zn、Ag、Sr、Al、Sb、W、Mn、V、Cr、Zr、Mo、Pd。在一种实施方案中,所述金属离子是溶剂化的。在一种实施方案中,所述金属离子用10-30%的异丙醇或作为替代的乙醇溶剂化。
在一种实施方案中,存在至少三种金属离子。优选地,所述三种金属离子彼此为1/1比率。
优选地,所述金属离子是Cu、Zn和Ag。
在一种实施方案中,所述悬浮液包含10-30%(w/v)的所述非晶态锡和0.1-0.5%(w/v)的所述一种或多种金属离子,任选溶剂化的。
在一种实施方案中,首先通过获得所述非晶态锡和Zn离子的水性悬浮液(被调节至碱性pH的溶液,优选用KOH),并且然后与包含nHA和Cu离子的溶液混合,并任选与包含Ag离子的碱性溶液混合来发生所述用掺杂的锡功能化。
在一种实施方案(Sn/Ti形式)中,所述功能化和取向的复合Ti与所述功能化和取向的Sn复合材料混合,从而获得功能化和取向的Ti/Sn复合材料。在一种实施方案中,所述功能化和取向的复合材料暴露于100°-150℃的温度下。
在一种实施方案中,将所述功能化的复合材料,任选在所述加热至100°-150℃之后施加在陶瓷半成品上从而产生涂覆的陶瓷半成品。作为实例,所述取向的功能化复合材料与一个或多个上釉涂敷同时施加,或与在成形步骤之后或在一个或多个上釉涂敷之间施加的釉底料混合。此外,在丝网印刷的工艺过程中,或在盐釉的工艺过程中(存在时)施加所述复合材料。通过实例的方式,所述复合材料与釉底料优选以10-50%w/v的比率混合,然后施加在陶瓷半成品上。所述釉底料选自陶瓷行业中已知的釉底料,其优选是包含高岭土、晶态二氧化硅和锆的混合物。所述釉底料通常以在460和880g/m2之间的量以在1200和1500g/升之间的密度(干当量:210-440g/m2)施加在陶瓷半成品上。作为替代或补充,在上釉步骤过程中例如以在100-300g/m2之间的量施加所述复合材料。
作为替代地,将所述功能化且取向的复合材料添加至陶瓷混合物,从而获得富化的陶瓷混合物。当所述功能化的复合材料与陶瓷混合物混合时,以10-50%w/v、优选20%的百分比添加所述功能化的复合材料。在模制之后,所述富化的陶瓷混合物产生包含取向的功能化复合材料的陶瓷半成品。
然后使包含取向的功能化复合材料的陶瓷半成品受到在600和1400℃之间、优选在900和1300℃之间的温度下的烘烤循环。
所述烘烤循环的持续时间与陶瓷半成品的厚度紧密相关,其中随着厚度提高烘烤时间变得越长。仅仅作为实例,具有10mm厚度的60×60砖需要约40分钟的烘烤循环。保持相同的表面积但提高厚度至20mm,需要的烘烤时间提高至约90分钟。
本发明的作者出乎预料地证明在所述烘烤之后,所述仿生材料和/或生物材料从纳米态转到纳米结构化的微米态。
如此获得的陶瓷材料有利地包含具有金红石的衍射极大值特性的晶态材料。在Ti形式实施方案中,图3A中的X-射线衍射谱图显示存在的主要相:金红石(R)、石英(Q)、莫来石(M)、钙长石(A)、硅灰石(W)。在Sn实施方案中,图4中的X-射线衍射谱图显示存在的主要相:锡石(图片A中的线)和钙长石(图片B中的线)。
如图5中对于Ti实施方案显示,使用扫描电子显微镜(SEM)的检查显示获得了具有纳米结构化的分级结构的羟基磷灰石微晶,其在表面处由金红石构成(图5B),表明烘烤将羟基磷灰石从纳米级改性到纳米结构化的微米级。颗粒都具有微米尺寸;分布范围从约1至100微米。在EDS微观分析中获得的谱图(5C)显示颗粒的元素组成由钙和磷以与羟基磷灰石的元素组成匹配(compatible)的比率组成。此外,标注了钛的信号和氧的信号。在不同点处分析的颗粒给出相同的组成,从而支持形成羟基磷灰石-金红石骨料的事实。
对于Sn实施方案,扫描电子显微镜(SEM)分析显示,如图6A中突出的,获得了具有纳米结构化的分级结构的羟基磷灰石的微晶,表明烧制将纳米尺寸的羟基磷灰石改性到微米级纳米结构化的。颗粒都具有微米尺寸;分布范围从约1至100微米。使用EDS微观分析获得的谱图(图6B)显示颗粒的元素组成由钙和磷以与羟基磷灰石的元素组成匹配的比率组成。还指出锡和氧信号。在不同点处分析的颗粒给出相同的组成,从而支持形成羟基磷灰石-锡石骨料的事实。
在另外的实施方案中,本发明涉及被赋予抗菌活性的光催化陶瓷材料,其中所述陶瓷材料的特征在于它包含具有纳米结构化的分级结构的羟基磷灰石微晶,所述纳米结构化的分级结构有宏观腔和微观腔。在所述微观腔内,以具有类金红石结构的晶态形式包括选自金属氧化物和/或硫化物的至少一种光催化剂。
在Ti实施方案中,所述陶瓷材料由如图3A中的X-射线衍射谱图和如图3B中通过“分布仪EDS”或EDS光谱法(能量色散X-射线光谱法)的方式获得在陶瓷材料中存在的原子的表面分布表征,所述“分布仪EDS”或EDS光谱法利用当加速的电子束撞击陶瓷样品时由加速的电子束产生的X射线的发射。图像突出了钛原子的定位基本上可叠加在磷和钙原子的定位上,其中所述磷和钙原子属于实际上用钛功能化的羟基磷灰石。
出于对比目的,对比了根据本发明的光催化陶瓷材料(Ti实施方案,图7中样品(a)曲线)的光催化活性与包含锐钛矿的商业光催化陶瓷材料(图7中样品(b)曲线)的光催化活性。
测试涉及测量在用汞蒸气灯照射材料之前和之后亚甲蓝的量。
表面样品(a)和(b)覆盖有等体积的1ppm亚甲蓝溶液并且将它们照射12小时。图7A中的图(曲线(a))显示根据本发明的陶瓷材料的出色的光催化活性。当延长照射至48小时时,差异仍然明显(图7B曲线a)。在两个图中曲线(c)显示被相同体积的1ppm亚甲蓝溶液覆盖的无光催化活性的表面。
通过用稳定且着色的污染物覆盖材料,具体地使用罗丹明B,并通过在用汞蒸汽灯照射材料之前和之后测量罗丹明B的量来评价根据Sn实施方案的光催化陶瓷材料的光催化活性。在照射之后根据本发明的光催化陶瓷材料上罗丹明的量减小表明根据本发明的陶瓷材料的异乎寻常的光催化活性。
出乎预料地,本发明人开发了创新的“生物启发”陶瓷材料和用于高效生产该材料的方法。
根据本发明的创新技术事实上设想单一烘烤步骤,即在第一烧制中烘烤一次。
使用根据本发明的技术,获得了在烘烤之后具有分级宏观和微孔结构的仿生微晶,所述微晶具有使它们极具反应性并可用于与金红石结合的形态和尺寸,所述金红石由所述微孔结构内部和外部的非晶态Ti开始结晶。获得的并在本文报道的实验数据显示根据本发明的陶瓷材料的高的光催化、抗菌和抗污染活性。在表征根据本发明的陶瓷材料的分级结构中存在的宏观腔和微观腔充当反应室或中心。当表面暴露于可见光中的波长时,在其中捕获并然后分解污染性有机物质。
在TiO2的已知晶态形式当中,金红石是热力学最稳定的天然形式,以及是在可见光中的波长下被活化的唯一形式。在制备过程中添加金属允许钛的掺杂,这在可见光区域中的波长下主要活化钛。
出乎预料地,本发明的作者显示了其它金属氧化物和/或硫化物例如SnO2如何能够在仿生材料中结晶,产生类金红石结构。
有利地,根据本发明的陶瓷随着时间没有失去抗菌和抗污染活性,因为沉积在陶瓷半成品上或添加至陶瓷混合物的nHA/非晶态金属经受在高温即大于600℃下的热处理,所述高温足以将其“焊接”到陶瓷,从而使其耐磨损。以下实施例仅出于更好地说明本发明的目的,并不理解为限制本发明,本发明的范围由权利要求限定。
实施例1:HA+Ti的合成(碱性水解)
羟基磷灰石nHA的制备:将16ml的1.35M氢氧化钙添加至70ml的水并用10ml的1.26M磷酸中和。用约4ml的1M氢氧化钠调节pH至11。获得基于纳米晶羟基磷灰石的水解悬浮液。
非晶态Ti的悬浮液:0.1-0.5%w/v的选自Cu、Zn、Ag、Sr、Al的一种或多种金属离子(用10-30%的异丙醇或作为替代的乙醇溶剂化)和10-30%w/v的非晶态Ti。
通过将所述非晶态Ti的悬浮液以20-60%w/v之间的量缓慢添加至所述水解悬浮液并同时剧烈搅拌从而获得用非晶态Ti功能化的nHA。
实施例2:TCP+Ti的合成(碱性水解)
羟基磷灰石β-TCP的制备,Ca/P比率1.30-1.55、优选1.51:将14ml的1.35M氢氧化钙添加至70ml的水并用10ml的1.26M磷酸中和。最终pH应在7和11之间,优选为8。获得水解悬浮液。
非晶态Ti的悬浮液:0.1-0.5%w/v的选自Cu、Zn、Ag、Sr、Al的一种或多种金属离子(用10-30%的异丙醇或作为替代的乙醇溶剂化)和10-30%w/v的非晶态Ti。
将所述非晶态Ti的悬浮液缓慢添加至所述水解悬浮液并同时剧烈搅拌,从而获得用非晶态Ti功能化的羟基磷灰石。
实施例3:透钙磷石合成(酸水解)
为了制备100ml的透钙磷石和/或三斜磷钙石(CaHPO4*2H2O(透钙磷石)和CaHPO4(三斜磷钙石))的悬浮液,将16ml的1.35M氢氧化钙添加至70ml的水并用10ml的1.26M磷酸中和。最终pH应在4和7之间,优选为6。非晶态Ti的悬浮液如以下构成:将0.1-0.5%w/v的Cu、Zn、Ag、Sr、Al中的一种金属离子或它们以1/1比率的混合物(并用10-30%的异丙醇或作为替代的乙醇溶剂化)和10-30%w/v的非晶态Ti缓慢添加至所述水解悬浮液并同时剧烈搅拌。
如此获得用无定形Ti功能化的nHA。
实施例4:合成HA+掺杂的Sn(碱性水解)
nHA羟基磷灰石的制备:将16ml的1.35M氢氧化钙添加至70ml的水并用10ml的1.26M磷酸中和。用约4ml的1M氢氧化钠调节pH至11。获得的是基于纳米晶羟基磷灰石的水解悬浮液。
非晶态Sn的悬浮液:0.1-0.5%w/v的选自Cu、Zn、Ag的一种或多种金属离子和10-30%w/v的非晶态Sn。
通过缓慢地并剧烈搅拌地以20-60%w/v之间组成的量添加所述非晶态Sn的悬浮液至所述水解悬浮液获得了用非晶态Sn功能化的nHA。
实施例5:HA+掺杂的Sn+Ti合成(碱性水解)
在混合器中以1:1比率添加从实施例4获得的用非晶态Sn功能化的nHA和从实施例1获得的用非晶态Ti功能化的nHA。
实施例6:与釉底料的混合物
将如来自实施例1-5的功能化nHA(其为功能化且取向的复合材料)以10-50%w/v百分比添加至釉底料混合物和以在460和880g/m2之间的量以在1200和1500g/升之间的密度(干当量:210-440g/m2)施加在陶瓷半成品上。所述釉底料包含高岭土、晶态二氧化硅、锆。然后将所述涂覆的陶瓷半成品在900和1300℃之间的温度下暴露于第一烧制中的烘烤。
当所述nHA是如实施例4中用非晶态Sn功能化的nHA,且所述陶瓷半成品为粗糙型时,获得定义为AR的陶瓷。
当所述nHA是如实施例1中用非晶态Ti功能化的nHA,且所述陶瓷半成品为粗糙型时,获得CR陶瓷。
当所述nHA是如实施例5中用非晶态Sn和非晶态Ti功能化的nHA,且所述陶瓷半成品为粗糙型时,获得BR陶瓷。
实施例7:采用盐釉的混合物
将如来自实施例1-5的功能化nHA(其为功能化且取向的复合材料)以10-50%w/v百分比添加至盐釉的混合物和以260-360g/m2的量以1100-1500g/升的密度(干当量:110-170g/m2)施加在尚未经受烘烤过程的陶瓷产品上。所述盐釉混合物包含陶瓷玻璃料、晶态二氧化硅、高岭土。然后将所述涂覆的陶瓷半成品在900和1300℃之间的温度下暴露于第一烧制中的烘烤。
当所述nHA是如实施例4中用非晶态Sn功能化的nHA,且所述陶瓷半成品为粗糙型时,获得AR陶瓷。
当所述nHA是如实施例1中用非晶态Ti功能化的nHA,且所述陶瓷半成品为粗糙型时,获得CR陶瓷。
当所述nHA是如实施例5中用非晶态Sn和非晶态Ti功能化的nHA,且所述陶瓷半成品为粗糙型时,获得BR陶瓷。
实施例8:抗菌活性
测试按照实施例6或7获得的AR陶瓷材料的抗菌活性。出于对比目的,使用在没有向釉底料添加功能化nHA的情况下烧制的相同陶瓷材料。用于测量光催化半导体材料的抗菌活性的方法按照ISO 27447:2019,使用聚丙烯膜。抗菌活性由UV照射之后在所分析的材料上发现的活细菌总数的对数和在黑暗中保存的相同材料上的活细菌总数的对数之间的差给出。通过18W汞蒸气UV灯提供照射,暴露时间为8小时。使用大肠杆菌,接种8.8×10e5CFU/ml。
获得的结果示于表1中并对于根据本发明的材料显示与未处理的材料相比在照射的情况下细菌活性降低等于99.4%。
表1
照射 | CFU/ml | |
未处理的材料(对比) | 否 | 16,400 |
未处理的材料(对比) | 是 | 1,700 |
AR材料 | 否 | 15,900 |
AR材料 | 是 | 10 |
实施例9:光催化活性、氧化一氮减少
使用切向流方法按照UNI 11484-2013标准进行NO减少测试。用简化的程序进行测试,即一旦达到在照射下测量的浓度的稳定条件或达到180分钟的最大照射时间,反应器内部的流速不变,因此结束在这些条件下的测试。在UV和可见光照射下都研究了样品。
通过APNA 370化学发光计的方式进行测量料流中NO/NO2含量的测定。测量反应器具有3.6dm3的内部容积。通过提供公称流量为70m3h-1的紧凑轴流风机EBMPAPST 612Jh(尺寸60×60×32mm)确保反应器内部混合。
使用一组两个Philips PL-S 9W/2P BLB荧光灯进行UV照射,该荧光灯在UV中具有显著的发射,其发射谱示于图8A中。在样品上入射的照射强度在290和400nm之间为10W m-2。
在可见光照射的情况下,尽管使用UNI 11484标准,但使用没有UV发射的LED照明器(6500K)。这一来源的谱图示于图8B中。在样品表面上的照度在400和800nm之间为250Wm-2。
使用配备余弦校正器的配备直径为400μm和长度为30cm的光纤的Ocean OpticsUSB2000+UV-VIS分光光度计(Ocean Optics CC-3-UV-T,PTFE光学扩散器,光谱范围200-2500nm,外径6.35mm,视场180°)通过分光辐射法(spectroradiometry)评价光强度。用Ocean Optics DH-2000-CAL氘-卤素光源灯校准分光辐射度仪,用于UV-Vis-NIR测量,其本身由销售商在绝对照度下校准(辐射校准标准UV-NIR,校准证书#2162)。
所测试样品是三个尺寸为9.9cm×9.9cm×10mm的陶瓷砖(分别称为AR、BR、CR)。三个样品由AR、BR、CR陶瓷组成,如在实施例6或7中获得。
在UV照射下,但在用软化水冲洗并在90℃干燥之后,对用于类似测试的样品进行按照UNI 11484标准但使用可见光照射的测试。
用各照射区域分析的样品列表示于表2中。
表2
测试期间NO和NO2浓度的演变示于图8中,其中图片C、D、E显示使用UV光曝光的数据,图片F、G和H显示使用可见光曝光的数据。
三个测试样品在UV和可见光辐射下均显示可测量的NO减少。
实施例10:光催化活性、罗丹明B测试
通过用稳定的着色(collared)污染物罗丹明B弄脏瓷砖,测量根据本发明的光催化陶瓷材料的光催化活性。然后将砖暴露于光源至多20小时的时间。从最开始的几个小时,光催化作用的结果看起来相当大。在图9中显示用汞蒸气灯照射材料之前和之后不同时间罗丹明B的量的测量结果,其中图片A的曲线显示根据本发明的AR陶瓷材料的令人惊奇的光催化活性,图片B的图显示污染物的降低如何随时间呈线性。
Claims (16)
1.用于生产抗菌光催化陶瓷的方法,其包括:
—制备可用的至少一种非晶态金属;
—制备可用的基于钙磷酸盐的仿生材料或生物材料;
—用所述至少一种非晶态金属将基于钙磷酸盐的所述仿生材料或所述生物材料功能化,从而获得功能化且取向的复合材料,其中取向的意为具有规则的晶体学排列;
—将所述功能化的复合材料添加至陶瓷混合物,和/或在陶瓷半成品上施加所述功能化的复合材料,其中陶瓷半成品意指烘烤之前的陶瓷材料;
—在600和1400℃之间、优选在900和1300℃之间的温度下烘烤持续从20至500分钟变化的时间,从而获得抗菌光催化陶瓷。
2.根据权利要求1所述的方法,其中所述至少一种金属选自包含以下的组:过渡金属和后过渡金属。
3.根据权利要求1或2中一项所述的方法,其中所述至少一种金属选自包含以下的组:钛、锡、锌、锆、镉、钨,优选钛、锡。
4.根据权利要求1或2中一项所述的方法,其中所述非晶态金属选自包含以下的组:硫酸氧钛(IV)、四氯化钛、四异丙氧基钛、异丙氧基钛、氯氧化钛、SnCl2、SnCl4、Sn(NO3)2、SnSO4、Sn(CH3SO3)2。
5.根据权利要求1至4中一项所述的方法,其中所述仿生材料或生物材料优选选自包含以下的组:透钙磷石、三斜磷钙石、羟基磷灰石(HA)、(β/α)磷酸三钙(TCP),并且在表面上缺少钙。
6.根据权利要求1至5中一项所述的方法,其中所述材料是仿生的并且是在7和14之间的pH、优选在pH 11下通过在剧烈搅拌下用磷酸逐滴中和氢氧化钙或醋酸钙或氯化钙或硝酸钙的悬浮液2-12小时而获得的纳米晶羟基磷灰石nHA。
7.根据权利要求6所述的方法,其中所述nHA具有在表面Ca/P之间范围为1.55-1.70、优选1.64的摩尔比。
8.根据权利要求1至7中一项所述的方法,其中通过将所述至少一种非晶态金属逐滴添加至在酸水解的情况(pH 1-6)下处于透钙磷石和/或三斜磷钙石形式或在碱性水解的情况(pH 7-14)下处于nHA或(β/α)TCP形式的钙磷酸盐的溶液来进行所述功能化。
9.根据权利要求1至8中一项所述的方法,其中使用掺杂的钛和/或掺杂的锡进行所述功能化,并且在悬浮液中逐滴添加所述非晶态Ti和/或Sn,所述悬浮液具有选自以下的一种或多种金属离子:Cu、Zn、Ag、Sr、Al、Sb、W、Mn、Sn、V、Cr、Zr、Mo、Pd。
10.根据权利要求9所述的方法,其中所述金属离子是溶剂化的。
11.根据权利要求1至10中一项所述的方法,其中所述取向的功能化复合材料与一个或多个上釉涂敷同时施加在陶瓷半成品上,或与在成形步骤之后施加的釉底料混合,或在一个或多个上釉涂敷之间施加,和/或在丝网印刷的工艺过程中施加,和/或在盐釉的工艺过程中施加。
12.抗菌光催化陶瓷材料,其包含基于钙磷酸盐的微晶仿生材料或生物材料,该微晶仿生材料或生物材料具有纳米结构化的分级结构,所述纳米结构化的分级结构有宏观腔和微观腔,在所述腔内处于具有类金红石结构的晶态形式的至少一种光催化剂选自金属氧和/或硫化物,所述金红石以有序方式排列,具有规则的晶体学排列。
13.根据权利要求12所述的抗菌光催化陶瓷材料,其中所述至少一种光催化剂选自TiO2、SnO2、ZnO、ZrO2、CdS和/或WO3。
14.根据权利要求11或12所述的抗菌光催化陶瓷材料,其中所述处于具有类金红石结构的晶态形式的至少一种光催化剂是TiO2、SnO2或它们的混合物。
15.抗菌光催化陶瓷材料,其由根据权利要求1至11的方法获得。
16.砖瓦、卫生器具、餐具,其包含根据权利要求12-15所述的光催化陶瓷材料。
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US11446644B2 (en) | 2022-09-20 |
US20220323642A1 (en) | 2022-10-13 |
IT201900015677A1 (it) | 2021-03-05 |
EP3789368A1 (en) | 2021-03-10 |
CN112441744A (zh) | 2021-03-05 |
US20210069681A1 (en) | 2021-03-11 |
BR112022003640A2 (pt) | 2022-05-24 |
MX2022002604A (es) | 2022-04-25 |
CA3152495A1 (en) | 2021-03-11 |
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WO2021044237A1 (en) | 2021-03-11 |
MA54199A (fr) | 2021-09-15 |
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