CN106082312B - 一种十四面体羟基锡酸盐及其制备方法和应用 - Google Patents
一种十四面体羟基锡酸盐及其制备方法和应用 Download PDFInfo
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- 150000003839 salts Chemical class 0.000 title claims abstract description 33
- VSKDLKJOZFLQQZ-UHFFFAOYSA-M O[Sn] Chemical compound O[Sn] VSKDLKJOZFLQQZ-UHFFFAOYSA-M 0.000 title claims abstract description 22
- 239000002253 acid Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 230000003750 conditioning effect Effects 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 238000007146 photocatalysis Methods 0.000 claims abstract description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
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- 239000010452 phosphate Substances 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 abstract description 4
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 4
- 229940071182 stannate Drugs 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 125000005402 stannate group Chemical group 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
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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
- B01J23/007—Mixed salts
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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
-
- 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
- B01J35/39—Photocatalytic properties
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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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明提供了一种十四面体羟基锡酸盐及其制备方法和应用，该十四面体羟基锡酸盐的分子式为MSn(OH)6，M为Ca、Mg、Co、Ni、Mn或Cu。其制备方法是将等摩尔的锡盐溶液和金属盐溶液混合，搅拌，加入调节剂，搅拌10min～3h，滴加碱溶液后转移至水热釜中反应5～24h，反应温度为25～120℃，即得。该十四面体羟基锡酸盐可广泛用于光催化技术领域，在光催化降解亚甲基蓝时十四面体光光降解效果优于六面体。
Description
技术领域
本发明属于光催化材料技术领域，具体涉及一种十四面体羟基锡酸盐及其制备方法和应用。
背景技术
羟基锡酸盐是典型的钙钛矿结构氢氧化物，具有优异的光催化、阻燃和抑烟等性能，是解决能源和环境问题的关键材料之一。由于羟基锡酸盐的形貌、尺寸以及组织结构对其阻燃性能和光催化性能具有重要影响，因此对不同形貌的羟基锡酸盐的控制合成引起了人们的广泛关注。目前，六面体规则形貌的MSn(OH)6(M=Ca、Mg、Co、Ni、Mn、Cu)已有了初步研究，但是十四面体羟基锡酸盐还鲜有报道。
发明内容
解决的技术问题：本发明的目的是克服现有技术的不足而提供一种十四面体羟基锡酸盐及其制备方法和应用，该十四面体羟基锡酸盐由于其裸露晶面不同于传统六面体结构，在光催化降解亚甲基蓝时十四面体光光降解效果优于六面体。
技术方案：一种十四面体羟基锡酸盐，其分子式为MSn(OH)6，M为Ca、Mg、Co、Ni、Mn或Cu，该羟基锡酸盐为十四面体结构。
所述十四面体羟基锡酸盐的制备方法，先将等摩尔的锡盐溶液和金属盐溶液混合，搅拌，加入调节剂，搅拌10min～3h，滴加碱溶液后转移至水热釜中反应5～24h，反应温度为25～120℃，即得。
进一步地，所述金属盐为钙盐、镁盐、钴盐、镍盐、锰盐或铜盐中的一种。
进一步地，所述调节剂为乙二胺、乙醇胺、二乙醇胺、三乙醇胺、磷酸盐、磷酸二氢盐或磷酸一氢盐中的一种或多种。
进一步地，所述碱溶液为NaOH、KOH、NH3•H2O中的一种或多种。
进一步地，锡盐与调节剂的摩尔比为1:1～1:3。
进一步地，碱与锡盐的摩尔比为1: 6～1: 18。
所述十四面体羟基锡酸盐在光催化技术领域的应用。
有益效果：
在羟基锡酸盐的制备过程中，调节剂可以与金属离子发生化学作用，一方面可有效地调控羟基锡酸盐的晶体生长过程，另一方面可定向地吸附在羟基锡酸盐的特定晶面上，从而诱导粒子最终向十四面体方向生长。
不同的晶面具有不同的表面原子排列密度，使得原子间的相互作用力也不一样，十四面体羟基锡酸盐由于其裸露晶面不同于传统六面体结构，在光催化降解亚甲基蓝时十四面体光光降解效果优于六面体。
附图说明
图1为实施例1的十四面体羟基锡酸钙的扫描电子显微镜图；
图2为实施例1的十四面体羟基锡酸钙与六面体羟基锡酸钙用于光催化降解亚甲基蓝的残留率曲线图。
具体实施方式
实施例1
将等摩尔的氯化锡溶液和醋酸钙溶液混合，搅拌均匀后于其中加入乙二胺和磷酸二氢钠两种调节剂，其量与锡盐的摩尔比为1:1，搅拌20 min，然后缓慢滴加一定量的NaOH溶液，碱与锡盐的摩尔比为1:7，并转移至水热釜中反应15h，反应温度为100℃。
如图1所示，所得十四面体羟基锡酸钙具有良好的形貌，且尺度规整。
将十四面体羟基锡酸钙与六面体羟基锡酸钙用于光催化降解亚甲基蓝，如图2所示，十四面体的光降解效果优于六面体结构。
实施例2
将等摩尔的氯化锡溶液和醋酸钴溶液混合，搅拌均匀后于其中加入三乙醇胺和磷酸钾两种调节剂，其量与锡盐的摩尔比为1:2，搅拌60 min，然后缓慢滴加一定量的NaOH溶液，碱与锡盐的摩尔比为1:6，并转移至水热釜中反应20h，反应温度为90℃。
应当理解的是，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，而所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (2)
1.一种十四面体羟基锡酸盐，其特征在于：其分子式为MSn(OH)6，M为Ca、Mg、Co、Ni、Mn或Cu，该羟基锡酸盐为十四面体结构；
其制备方法是将等摩尔的锡盐溶液和金属盐溶液混合，搅拌，加入调节剂，搅拌10min～3h，滴加碱溶液后转移至水热釜中反应5～24h，反应温度为25～120℃，即得；
所述金属盐为钙盐、镁盐、钴盐、镍盐、锰盐或铜盐中的一种；
所述调节剂为乙二胺、乙醇胺、二乙醇胺、三乙醇胺、磷酸盐、磷酸二氢盐或磷酸一氢盐中的一种或多种；
所述碱溶液为NaOH、KOH、NH3•H2O中的一种或多种；
锡盐与调节剂的摩尔比为1:1～1:3；
碱与锡盐的摩尔比为1: 6～1: 18。
2.权利要求1所述的十四面体羟基锡酸盐在光催化技术领域的应用。
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| CN107185556B (zh) * | 2017-06-01 | 2020-03-17 | 合肥工业大学 | 一种基于非贵金属过渡元素硫化物的高效光催化剂的制备方法 |
| CN107224978B (zh) * | 2017-07-24 | 2019-08-09 | 福州大学 | 羟基锡酸钴/石墨烯复合光催化剂的制备方法及其应用 |
| US10808193B2 (en) | 2019-03-08 | 2020-10-20 | King Fahd University Of Petroleum And Minerals | Cobalt hydroxystannate nanocube fuel additive |
| CN112142097B (zh) * | 2020-08-31 | 2021-10-29 | 武汉理工大学 | 三水合锡酸镉及其制备方法和应用 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0524832A (ja) * | 1991-07-16 | 1993-02-02 | Mitsubishi Materials Corp | 高純度ヒドロキシ錫酸亜鉛粉末の製造方法 |
| JP2002502459A (ja) * | 1997-06-04 | 2002-01-22 | アルキャン・インターナショナル・リミテッド | スズ酸二価金属塩生成物 |
| CN103990446A (zh) * | 2014-05-16 | 2014-08-20 | 淮北师范大学 | 一种Sn基氢氧化物型光催化剂及其制备方法和应用 |
| CN104150527A (zh) * | 2014-06-24 | 2014-11-19 | 济南大学 | 一种空心十四面体结构羟基锡酸锌气敏材料的制备方法 |
-
2016
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0524832A (ja) * | 1991-07-16 | 1993-02-02 | Mitsubishi Materials Corp | 高純度ヒドロキシ錫酸亜鉛粉末の製造方法 |
| JP2002502459A (ja) * | 1997-06-04 | 2002-01-22 | アルキャン・インターナショナル・リミテッド | スズ酸二価金属塩生成物 |
| CN103990446A (zh) * | 2014-05-16 | 2014-08-20 | 淮北师范大学 | 一种Sn基氢氧化物型光催化剂及其制备方法和应用 |
| CN104150527A (zh) * | 2014-06-24 | 2014-11-19 | 济南大学 | 一种空心十四面体结构羟基锡酸锌气敏材料的制备方法 |
Non-Patent Citations (2)
| Title |
|---|
| Controlled Growth and Applications of Complex Metal Oxide ZnSn(OH)6 Polyhedra;Jingzhou Yin et al.;《Inorganic Chemistry》;20121002;第51卷;摘要，10990页右栏第2段，第10991页表1、左栏最后一段，第10992页图4e、4f，10994页左栏最后一段 * |
| Ionic transport and structural investigations on MSn(OH)6 (M=Ba, Ca, Mg, Co, Zn, Fe, Mn) hydroxide perovskites synthesized by wet sonochemical methods;Hrudananda Jena et al.;《Materials Chemistry and Physics》;20041231;第88卷;第168页第2.1节 * |
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