CN105561969B - 一种多孔TixSn1-xO2固溶体微球的制备和应用 - Google Patents
一种多孔TixSn1-xO2固溶体微球的制备和应用 Download PDFInfo
- Publication number
- CN105561969B CN105561969B CN201610116919.6A CN201610116919A CN105561969B CN 105561969 B CN105561969 B CN 105561969B CN 201610116919 A CN201610116919 A CN 201610116919A CN 105561969 B CN105561969 B CN 105561969B
- Authority
- CN
- China
- Prior art keywords
- solid solution
- porous
- preparation
- microballoon
- iii
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000006104 solid solution Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000010936 titanium Substances 0.000 claims abstract description 53
- 229910008598 TixSn1−xO2 Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- BLOIXGFLXPCOGW-UHFFFAOYSA-N [Ti].[Sn] Chemical compound [Ti].[Sn] BLOIXGFLXPCOGW-UHFFFAOYSA-N 0.000 abstract description 5
- 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 abstract description 3
- 229910052785 arsenic Inorganic materials 0.000 description 16
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 238000007704 wet chemistry method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 hydroxyl radical free radical Chemical class 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种多孔TixSn1‑xO2固溶体微球的制备和应用,其采用钛酸四正丁酯或者异丙醇钛为钛源,可溶性锡盐为锡源,无水乙醇或者异丙醇为溶剂,控制反应体系的总浓度为4‑10mmol/70mL。首次采用溶剂热法,得到Ti/Sn比例可调,多孔球状结构较为规则的钛锡固溶体TixSn1‑xO2材料(0<x<1.0);特别地,采用本发明的方法能制得0.33<x<0.67的材料。另外本发明将制备的多孔TixSn1‑xO2固溶体微球应用于光催化氧化除As(III)中,表现出优秀的光催化活性,且对于As(V)也表现出了较好的吸附作用,可以减少后续处理中加入絮凝剂的量,在一定程度上降低了水体的二次污染。
Description
技术领域
本发明属于材料制备领域,具体涉及一种多孔TixSn1-xO2固溶体微球材料的制备和应用。
背景技术
SnO2和TiO2材料广泛用作催化剂、气敏传感器、吸附材料和微波介电陶瓷等。SnO2和TiO2均有金红石结构,且晶格常数相近(SnO2:a = 0.4738 nm,c = 0.3188 nm;TiO2:a =0.4539 nm,c = 0.2959 nm),因而可形成TixSn1-xO2固溶体。由于复合氧化物在某些特性上优于单一氧化物,所以TixSn1-xO2固溶体是目前研究的热点,尤其在光催化剂、敏感器件和锂电池电极上的应用近年来取得了较大的进展。TixSn1-xO2固溶体的性质不仅与x值有关,而且也与其材料形貌结构密切相关,开发0≤x≤1.0全范围的TixSn1-xO2固溶体的简易制备方法,并制备具有特殊多孔球状结构型的TixSn1-xO2固溶体,将有助于拓展此类固溶体的应用范围。
由于传统湿化学法制备钛锡固溶体受x值的限制,在x ≥ 0.67和x ≤ 0.33的范围内可以形成TixSn1-xO2固溶体,而当x=0.5时,却难以形成固溶体。不仅如此,湿化学法制备的钛锡固溶体过程中,还需要对混合物进行后续的热处理工艺才能制备出固溶体材料,在工艺上存在不足,而且制备的材料不具备多孔球状结构的形貌。
地表水中的砷主要以三价砷(As(Ⅲ))和五价砷(As(Ⅴ))两种形式存在。目前,常用于污染废水中除砷的工艺主要有:离子交换法,反渗透法,混凝沉淀法和吸附法等,然而这些工艺也存在缺陷,譬如吸附法,常用的吸附剂为活性炭和氧化铝,但由于As(Ⅲ)流动性强而较As(Ⅴ)不易去除,且这些吸附剂对As(Ⅲ)的吸附作用较As(Ⅴ)差,然而三价砷毒性是五价砷毒性的的100倍。因此在吸附之前需要先实施预处理将高毒性的As(Ⅲ)氧化为低毒性的As(Ⅴ);再将As(Ⅴ)吸附去除。现已报道的氧化As(III)的方法有MnO2氧化法, UV/Fe3+氧化法, H2O2氧化法,O2/O3氧化法和光催化氧化法等。其中,光催化氧化技术作为一种新兴的环境治理技术,因其反应条件温和,无二次污染以及利用天然的太阳光驱动反应的特点,在氧化As(III)污染物方面发挥着重要作用。相关研究结果表明,光催化剂可通过产生光生空穴(hvb +)直接氧化高毒性的As(III)成低毒的As(V),也可通过产生光生电子(e−)并与H2O、O2反应生成过具有强氧化性的氧化氢(H2O2)、羟基自由基(·OH)或超氧自由基(·O2 −)等强氧化性物种而起氧化作用。这些研究结果无疑从原理上证明了光催化氧化技术在水中砷化物治理中的可行性。然而,TiO2的量子效率低,活性不好等问题制约了其在光催化除砷技术中的实际应用,因此开发对As(III)具有高效氧化能力的新型光催化剂显得尤为重要。而半导体复合主要是利用能级宽度不同的但又相近的两种半导体负荷,不仅可以使光生载流子在不同能级载流子之间运输,延长了载流子的寿命,避免载流子的分离,从而提高了体系的光催化活性。
因此,我们利用简易的溶剂热方法,对TixSn1-xO2固溶体中的组分x进行调变,制备出组分连续可调的钛锡固溶体材料,并且其在光催化氧化除砷方面也表现出了一定实用价值。
发明内容
本发明的目的在于针对现有技术的不足,提供一种多孔TixSn1-xO2固溶体微球光催化剂的制备和应用。TixSn1-xO2固溶体的传统制备方法为湿化学法,有别于传统的湿化学法的缺点,我们利用较为简易的溶剂热法制备出的TixSn1-xO2固溶体Ti/Sn比例可调,多孔球状结构较为规则;特别地,采用本发明的方法能制得0.33<x<0.67的材料。
为实现上述发明目的,本发明采用如下技术方案:
一种多孔TixSn1-xO2固溶体微球的制备方法,采用溶剂热法制得Ti/Sn比例可调的多孔TixSn1-xO2固溶体微球,其中0<x<1.0。
特别的,所述的多孔TixSn1-xO2固溶体微球,0.33<x<0.67。
所述的制备方法,具体步骤为:
(1)以钛酸正四丁酯、异丙醇钛、四氯化钛或者硫酸钛作为钛源,可溶性锡盐(IV)作为锡源,以异丙醇或者无水乙醇作为溶剂,调节Ti源和Sn源摩尔比例,控制反应釜中的原料的总浓度在4-10mmol/70mL;
(2)将反应釜置于140-200℃烘箱中保温6-24h,得到白色浑浊液,经离心、乙醇洗涤、60℃烘干、研磨可得到x连续可调的多孔球状结构的TixSn1-xO2固溶体白色粉末材料。
一种如上所述的制备方法制得的多孔TixSn1-xO2固溶体微球在光催化剂中的应用。
具体的:在紫外光照射下,多孔TixSn1-xO2固溶体微球作为将As(III)氧化为As(V)的光催化剂。
我们将制备的多孔TixSn1-xO2固溶体微球应用于光催化氧化除As(III)中,相比于单一的传统的除砷光催化剂TiO2,多孔TixSn1-xO2固溶体微球这种复合材料在光催化氧化除As(III)中表现出优秀的光催化活性,且对于光催化氧化As(III)产生的As(V)也表现出了较好的吸附作用,可以减少后续处理中加入絮凝剂的量,在一定程度上降低了水体的二次污染。
本发明的显著优点在于:
(1)本发明首次采用溶剂热法合成出x取值范围在0.33~0.67的多孔TixSn1-xO2固溶体微球;弥补了传统湿化学法制备钛锡固溶体受x值的限制,只能在x ≥ 0.67和x ≤ 0.33的范围内可以形成TixSn1-xO2固溶体的不足;
(2)本发明将所制备的带有多孔结构的TixSn1-xO2固溶体微球应用于光催化氧化处理As(III)污染废水领域,可有效将高毒性的As(III)氧化为低毒性的As(V),并且能将氧化产生的As(V)在一定程度上大量吸附;
(3)本发明的多孔TixSn1-xO2固溶体微球光催化剂制备方法简单易行,有利于大规模的推广。
附图说明
图1展示了本发明不同Ti/Sn比例TixSn1-xO2固溶体的X射线衍射(XRD)图,从图中可以发现制备出的TixSn1-xO2为单一晶相;
图2-1、图2-2、图2-3展示了本发明不同Ti/Sn比例TixSn1-xO2固溶体的场发射扫描电镜(SEM)图,从图中可看到TixSn1-xO2呈现出较为规则的多孔球状结构;图2-1(Ti0.3Sn0.7O2),图2-2(Ti0.5Sn0.5O2),图2-3(Ti0.7Sn0.3O2);
图3-1、图3-2、图3-3展示了本发明不同Ti/Sn比例TixSn1-xO2固溶体的的透射电镜(TEM)图,从图中可看到TixSn1-xO2呈现出较为规则的多孔球状结构;图3-1(Ti0.3Sn0.7O2),图3-2(Ti0.5Sn0.5O2),图3-3(Ti0.7Sn0.3O2);
图4是本发明的光催化剂Ti0.5Sn0.5O2固溶体在含砷水体中光催化氧化As(III)的活性图,以及水体中总As(III)随时间的变化情况;曲线a 是TixSn1-xO2固溶体对As(Ⅲ)的暗吸附情况,曲线b是在紫外光照射下,Ti0.5Sn0.5O2固溶体光催化剂存在时,As(Ⅲ)的降解情况;曲线c是光照下Ti0.5Sn0.5O2固溶体光催化剂存在时,水体中总砷随时间的变化情况。
具体实施方式:
多孔TixSn1-xO2固溶体微球的制备方法,步骤如下:
(1)用钛酸正四丁酯、异丙醇钛、四氯化钛或者硫酸钛作为钛源,可溶性锡盐(IV)作为锡源,以异丙醇或者无水乙醇作为溶剂,调节Ti源和Sn源摩尔比例,控制反应釜中的原料的总浓度在4-10mmol/70mL之间;
(2)将反应釜置于140-200℃烘箱中保温6-24h,得到白色浑浊液,经离心、乙醇洗涤、60℃烘干、研磨可得到组分x连续可调的多孔TixSn1-xO2固溶体微球白色粉末材料。
以下是本发明的几个实施例,进一步说明本发明,但是本发明不仅限于此。
实施例1
多孔TixSn1-xO2固溶体微球的制备:
将 (0.0018mol)钛酸正四丁酯和(0.0042 mol) SnCl4·5H2O溶于70mL异丙醇中,搅拌30分钟得到混合溶液;随后将混合溶液置于100ml高压反应釜内,搅拌10分钟后,将反应釜置于180℃烘箱中,保温12h。得到白色浑浊液,离心、乙醇洗涤、60℃烘干、研磨得到白色的Ti0.3Sn0.7O2粉末。
实施例2
多孔TixSn1-xO2固溶体微球的制备:
将 (0.0025mol)钛酸正四丁酯和(0.0025 mol) SnCl4·5H2O溶于70mL异丙醇中,搅拌30分钟得到混合溶液;随后将混合溶液置于100ml高压反应釜内,搅拌10分钟后,将反应釜置于180℃烘箱中,保温12h。得到白色浑浊液,离心、乙醇洗涤、60℃烘干、研磨得到白色的Ti0.9Sn0.1O2粉末。
实施例3
多孔TixSn1-xO2固溶体微球的制备:
将 (0.0042mol)钛酸正四丁酯和(0.0018 mol) SnCl4·5H2O溶于70mL异丙醇中,搅拌30分钟得到混合溶液;随后将混合溶液置于100ml高压反应釜内,搅拌10分钟后,将反应釜置于180℃烘箱中,保温12h。得到白色浑浊液,离心、乙醇洗涤、60℃烘干、研磨得到白色的Ti0.7Sn0.3O2粉末。
实施例1-3所得产物均为TixSn1-xO2固溶体材料,均具有相似的XRD谱图和SEM谱图,只是XRD谱图中衍射峰的强度、位置、以及半峰宽略有差别。SEM、TEM谱图中的多孔球状颗粒大小有些差别。
实施例4
光催化剂Ti0.5Sn0.5O2处理砷污染水体的应用:
将得到的Ti0.5Sn0.5O2粉末用作光催化剂降解As(III),称取80mg样品加入80mL As(III)溶液(2mg/L),然后开启光源进行光催化反应,每隔一定时间取2mL反应液,经离心分离后,分为两份, 分别用2~3wt%HCL稀释,记做As(III);和含1 wt%的硫脲和抗坏血酸的盐酸溶液稀释(将氧化生成的As(Ⅴ)重新还原为As(Ⅲ))记做总砷。用PF6非散射原子荧光分光光度检测As(Ⅲ)和总砷的浓度。As(Ⅲ)的降解情况如图4所示,从图上可以看出在没有光催化剂Ti0.5Sn0.5O2存在时,仅仅紫外光照射,As(III)浓度基本不变(曲线a),说明在紫外光下As(V)能稳定存在。而Ti0.5Sn0.5O2的暗吸附情况如曲线(b)所示,其对于高浓度的As表现出一定的吸附作用,这有利于光催化氧化反应的发生。而在紫外光照射下,光催化剂Ti0.5Sn0.5O2存在时,As(Ⅲ)在光照40min后基本完全降解(曲线c)。此外,被硫脲和抗坏血酸还原后的总砷经40min后,93.5%被吸附(曲线d),说明Ti0.5Sn0.5O2对As(III)氧化生成的As(Ⅴ)有较好的吸附作用。因此,Ti0.5Sn0.5O2可作为有效去除砷污染水体的的光催化剂。
Claims (3)
1.一种多孔TixSn1-xO2固溶体微球的制备方法,其特征在于:采用溶剂热法制得Ti/Sn比例可调的多孔TixSn1-xO2固溶体微球,其中0<x<1.0;具体步骤为:(1)以钛酸正四丁酯、异丙醇钛、四氯化钛或者硫酸钛作为钛源,可溶性IV价锡盐作为锡源,以异丙醇或者无水乙醇作为溶剂,调节Ti源和Sn源摩尔比例,控制反应釜中的原料的总浓度在4-10mmol/70mL;
(2)将反应釜置于140-200℃烘箱中保温6-24h,得到白色浑浊液,经离心、乙醇洗涤、60℃烘干、研磨可得到x连续可调的多孔球状结构的TixSn1-xO2固溶体白色粉末材料。
2.根据权利要求1所述的制备方法,其特征在于:所述的多孔TixSn1-xO2固溶体微球,0.33<x<0.67。
3.一种如权利要求1或2所述的制备方法制得的多孔TixSn1-xO2固溶体微球在光催化剂中的应用,其特征在于:在紫外光照射下,多孔TixSn1-xO2固溶体微球作为将III 价As氧化为V 价As的光催化剂。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610116919.6A CN105561969B (zh) | 2016-03-02 | 2016-03-02 | 一种多孔TixSn1-xO2固溶体微球的制备和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610116919.6A CN105561969B (zh) | 2016-03-02 | 2016-03-02 | 一种多孔TixSn1-xO2固溶体微球的制备和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105561969A CN105561969A (zh) | 2016-05-11 |
CN105561969B true CN105561969B (zh) | 2018-06-29 |
Family
ID=55872925
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610116919.6A Expired - Fee Related CN105561969B (zh) | 2016-03-02 | 2016-03-02 | 一种多孔TixSn1-xO2固溶体微球的制备和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105561969B (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108393098B (zh) * | 2018-03-22 | 2020-09-18 | 江苏三剂实业有限公司 | 一种低温脱硝催化剂及其制备方法 |
CN108987712B (zh) * | 2018-07-20 | 2021-10-01 | 福建师范大学 | 一种钠离子电池负极材料的制备方法 |
CN115072772A (zh) * | 2022-06-14 | 2022-09-20 | 山西农业大学 | 一种球形核壳结构锡钛氧化物的制备方法、产品及应用 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102671649A (zh) * | 2012-04-05 | 2012-09-19 | 沈阳化工大学 | 一种饮用水除砷(iii)纳米光催化氧化剂的制备方法 |
CN103648984B (zh) * | 2012-06-14 | 2017-02-22 | 松下知识产权经营株式会社 | 对含砷水溶液进行处理的方法 |
CN102992398B (zh) * | 2012-12-18 | 2014-08-27 | 中国科学院合肥物质科学研究院 | 二氧化钛-二氧化锡纳米固溶体材料的制备方法 |
CN103117174B (zh) * | 2013-03-20 | 2016-04-06 | 宁波大学 | 染料敏化太阳能电池光阳极及利用该光阳极制备染料敏化纳米晶太阳能电池的方法 |
CN105355900B (zh) * | 2015-12-01 | 2017-08-08 | 福建江夏学院 | 具有高比例101晶面的锡钛复合氧化物及其制备方法 |
-
2016
- 2016-03-02 CN CN201610116919.6A patent/CN105561969B/zh not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN105561969A (zh) | 2016-05-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Duan et al. | TiO2 faceted nanocrystals on the nanofibers: Homojunction TiO2 based Z-scheme photocatalyst for air purification | |
Chen et al. | Characterization and photoreactivity of N-, S-, and C-doped ZnO under UV and visible light illumination | |
Ohno et al. | Photocatalytic activity of S-doped TiO2 photocatalyst under visible light | |
Wang et al. | Preparation of Ti3+ self-doped TiO2 nanoparticles and their visible light photocatalytic activity | |
Li et al. | Photocatalytic degradation of methyl orange in a sparged tube reactor with TiO2-coated activated carbon composites | |
CN113663693B (zh) | 一种硫化铟锌-二氧化钛复合材料的制备方法及其在生产双氧水用于废水治理中的应用 | |
Zhou et al. | Experimental study on photocatalytic activity of Cu 2 O/Cu nanocomposites under visible light | |
CN112156803B (zh) | 光催化复合材料及其制备方法和应用 | |
CN101844077B (zh) | 具有可见光活性的碳氮改性纳米二氧化钛薄膜的制备方法 | |
CN102580742A (zh) | 一种活性炭负载氧化亚铜光催化剂及其制备方法 | |
CN110152711A (zh) | 一种CeO2@MoS2/g-C3N4三元复合光催化剂及其制备方法 | |
CN108187687B (zh) | 一种光芬顿催化剂的制备方法 | |
CN106732504A (zh) | 石墨烯二氧化钛光催化复合材料的制备方法及应用 | |
CN105561969B (zh) | 一种多孔TixSn1-xO2固溶体微球的制备和应用 | |
CN105536843A (zh) | 高可见光电子转移g-C3N4/Au/TiO2类Z型光催化剂的制备方法 | |
Junploy et al. | Photocatalytic activity of Zn2SnO4–SnO2 nanocomposites produced by sonochemistry in combination with high temperature calcination | |
CN115301225A (zh) | 一种中空微球结构的铋/二氧化钛光催化降解材料的制备方法及其应用 | |
Channei et al. | Adsorption and photocatalytic processes of mesoporous SiO2-coated monoclinic BiVO4 | |
Tavakoli-Azar et al. | Enhanced photocatalytic activity of ZrO2-CdZrO3-S nanocomposites for degradation of Crystal Violet dye under sunlight | |
CN107469822A (zh) | 高效电子转移Cu修饰C/TiO2光催化还原材料的制备方法 | |
Dao et al. | Highly photocatalytic activity of pH-controlled ZnO nanoflakes | |
Albouyeh et al. | The green synthesis of magnesium oxide nanoparticles in MFI type zeolite and its application as a photocatalyst | |
CN103506104B (zh) | 玻璃片载体上碳掺杂TiO2可见光响应催化膜及其制备方法 | |
CN113101980A (zh) | 一种具有可见光催化活性的TiO2/UiO-66复合材料的制备方法和应用 | |
Zhang et al. | Carbon-dot-modified TiO 2− x mesoporous single crystals with enhanced photocatalytic activity for degradation of phenol |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180629 Termination date: 20210302 |