CN109046455B - 一种混配型杂多酸有机-无机化合物,制备方法及其在可见光催化降解染料废水中的应用 - Google Patents
一种混配型杂多酸有机-无机化合物,制备方法及其在可见光催化降解染料废水中的应用 Download PDFInfo
- Publication number
- CN109046455B CN109046455B CN201810980354.5A CN201810980354A CN109046455B CN 109046455 B CN109046455 B CN 109046455B CN 201810980354 A CN201810980354 A CN 201810980354A CN 109046455 B CN109046455 B CN 109046455B
- Authority
- CN
- China
- Prior art keywords
- heteropoly acid
- inorganic compound
- mixed
- acid organic
- visible light
- 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.)
- Active
Links
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 35
- 229910010272 inorganic material Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002351 wastewater Substances 0.000 title abstract description 15
- 230000015556 catabolic process Effects 0.000 title abstract description 12
- 238000006731 degradation reaction Methods 0.000 title abstract description 12
- 230000003197 catalytic effect Effects 0.000 title abstract description 6
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910004160 TaO2 Inorganic materials 0.000 claims description 5
- NQKXFODBPINZFK-UHFFFAOYSA-N dioxotantalum Chemical compound O=[Ta]=O NQKXFODBPINZFK-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 239000010949 copper Substances 0.000 abstract description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 239000011941 photocatalyst Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- 125000005842 heteroatom Chemical group 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 description 8
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 239000001045 blue dye Substances 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- 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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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
Abstract
本发明公开了一种混配型杂多酸有机‑无机化合物,制备方法及其在可见光催化降解染料废水中的应用,属于混配型杂多酸的合成及其光催化降解染料废水技术领域。本发明的技术方案要点为:一种混配型杂多酸有机‑无机化合物,以过渡金属铜为杂原子通过Cu‑N键链接4,4´‑联吡啶,其分子式为[Cu2(C10N2H8)][Cu(C10N2H8)2]4[P2W15Ta3O62]2•13H2O,其晶体结构单元如图1所示。本发明还具体公开了该混配型杂多酸有机‑无机化合物的制备方法及其在可见光催化降解染料废水中的应用。本发明合成过程简单且成本低廉;不溶于水,利于光催化剂的回收与循环;在紫外光区和可见光区均有吸收,在污水处理、有机物降解等应用方面的应用前景广泛。
Description
技术领域
本发明属于混配型杂多酸的合成及其光催化降解染料废水技术领域,具体涉及一种混配型杂多酸有机-无机化合物,制备方法及其在可见光催化降解染料废水中的应用。
背景技术
在21世纪,能源与环境问题已经成为世界关注的主题,如何减少污染,保护生态平衡,解决环保问题,已经引起各政府决策部门和学术研究部门的高度重视。水和空气作为人类最宝贵的资源,随着工业进程的加快,大量的废水、废弃被排入其中,其中的有毒有机化合物会在人体内富集,给健康带来巨大威胁。因此,开发新能源、降解污染物成为亟待解决的问题。开发有效的光催化剂、发展光催化技术是解决目前人们面临的能源和环境问题的有效途径之一。光催化处理有机污染物的技术由于其价格低廉、无毒、节能、高效的优势逐渐成为各界人士研究的重点,光催化也被认为是治理环境污染最有效的途径之一。
混配型杂多酸因其在光催化产氢及光催化降解污染物等方面的潜在应用,成为多酸化学领域的研究热点。但大多数多酸化合物极易溶于水,具有较大的禁带宽度,仅能利用紫外光,太阳光中仅含有少量的紫外光,这严重阻碍了多酸作为光催化材料的进一步开发与应用。因此,探索和发展难溶的且在可见光下具有光催化活性的混配型杂多酸材料具有重要的科学意义。
发明内容
本发明解决的技术问题是提供了一种混配型杂多酸有机-无机化合物及其制备方法,该方法是以过渡金属与有机配体形成的混配型杂多酸,其在可见光下具有良好的光催化活性,能够用于在可见光下催化降解染料废水。
本发明为解决上述技术问题采用如下技术方案,一种混配型杂多酸有机-无机化合物,其特征在于:该混配型杂多酸有机-无机化合物以过渡金属铜为杂原子通过Cu-N键链接4,4´-联吡啶,其分子式为[Cu2 (C10N2H8)][Cu (C10N2H8)2]4[P2W15Ta3O62]2•13H2O,其晶体结构单元如图1所示,该化合物是以两个Dawson型多酸与六个铜离子九个4,4´-联吡啶形成,通过两个平行的4,4´-联吡啶形成孔状结构。由于Ta是+5价而W是+6价,所以Ot(Ta)比Ot(W)的亲核性更强。在化合物中,Cu原子都通过N-Cu-Ot(Ta)连接在TaO6八面体上,每个Cu原子都是五配位,经价键计算得所有Cu均为+2价。
本发明所述的混配型杂多酸有机-无机化合物的制备方法,其特征在于具体步骤为:
步骤S1:将前驱体K5Na4[P2W15(TaO2)3]•17H2O、NaHSO3和H2O形成的混合溶液于75℃搅拌30min,再依次加入4,4´-联吡啶和CuSO4,然后用1mol/L的盐酸溶液调节混合体系的pH值为2~3,搅拌混合均匀得到混合液;
步骤S2:将步骤S1得到的混合液转移至水热反应釜中,再将该水热反应釜置于可程序控温的烘箱中,设定烘箱的温度参数,1h从室温升温至160℃,于160℃保温72h,然后于48h降温至30℃,最终得到绿色块状晶体即混配型杂多酸有机-无机化合物。
优选的,步骤S1中所述K5Na4[P2W15(TaO2)3]•17H2O、NaHSO3、4,4´-联吡啶与CuSO4的投料质量比为0.2:0.04:0.06:0.2。
本发明所述的混配型杂多酸有机-无机化合物在可见光催化降解染料废水中的应用,其特征在于具体过程为:向石英光催化反应管中加入50mL质量浓度为5mg/L的亚甲基蓝染料废水,再加入40mg混配型杂多酸有机-无机化合物,然后从石英光催化反应管的底部通入恒流量的空气,用300W的氙灯照射至少80min完成光催化降解亚甲基蓝染料废水的过程,其光催化降解率达到96.9%以上。
本发明与现有技术相比具有以下优点:
1、其合成过程简单且成本低廉;
2、不溶于水,利于光催化剂的回收与循环;
3、在紫外光区和可见光区均有吸收,在污水处理、有机物降解等应用方面的应用前景广泛。
附图说明
图1是实施例1制得的混配型杂多酸有机-无机化合物的晶体结构图;
图2是实施例1制得的混配型杂多酸有机-无机化合物的粉末XRD图谱;
图3是实施例1制得的混配型杂多酸有机-无机化合物的红外光谱图;
图4是实施例1制得的混配型杂多酸有机-无机化合物的固体漫反射光谱;
图5是实施例1制得的混配型杂多酸有机-无机化合物光催化降解亚甲基蓝溶液中降解时间与吸光度的关系曲线,催化剂的用量为0.8g/L。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明,但不应该将此理解为本发明上述主题的范围仅限于以下的实施例,凡基于本发明上述内容实现的技术均属于本发明的范围。
实施例1
混配型杂多酸有机-无机化合物的制备
步骤S1:将前驱体K5Na4[P2W15(TaO2)3]•17H2O(0.2g, 0.04mmol)、NaHSO3(0.04g,0.38mmol)及H2O(10mL)形成的混合溶液于75℃搅拌30min,再依次向溶液中加入4,4´-联吡啶(0.06g, 0.03mmol)和CuSO4(0.2g, 0.08mmol),然后用1mol/L的盐酸溶液将混合体系的pH值调至2~3,搅拌混合均匀得到混合液;
步骤S2:将步骤S1得到的混合液转移至水热反应釜中,再将该水热反应釜置于可程序控温的烘箱中,设定烘箱的温度参数,1h从室温升温至160℃,于160℃保温72h,然后于48h降温至30℃,最终得到绿色块状晶体即混配型杂多酸有机-无机化合物,产率为54%。
图1是本实施例制得的混配型杂多酸有机-无机化合物的晶体结构图,图中深灰色色四方锥代表WO6,黑色八面体代表TaO6,黑色球代表Cu原子,白色球代表C原子,灰色球代表N原子,深灰色球代表O原子。
图2是本实施例制得的混配型杂多酸有机-无机化合物的粉末XRD曲线,实验数据与单晶模拟数据能够很好地吻合,说明了制得的粉末样品具有较高的纯度。
图3是本实施例制得的混配型杂多酸有机-无机化合物的红外光谱图,其中1610cm-1处出现的强峰可以认为是化合物的晶格水和配位水分子的振动;在1088cm-1、951cm-1、913cm-1、770cm-1和523cm-1出现的特征峰,可归结为Dawson型多阴离子[P2W15(TaO2)3]9-中的Vas(P-Oa)、Vas(W=Ot)、Vas(W-Ob)和Vas(W-Oc)的特征吸收峰;化合物的1536cm-1、1492cm-1、1416cm-1和1220cm-1峰可认为是4,4´-联吡啶的特征吸收峰。
图4是本实施例制得的混配型杂多酸有机-无机化合物的固体漫反射光谱所示,所制备的目标产物在紫外光区和可见光区均有吸收。
实施例2
光催化降解染料废水的活性测试
向石英光催化反应管中加入50mL质量浓度为5mg/L的亚甲基蓝溶液,然后加入40mg实施例1制得的混配型杂多酸有机-无机化合物,再从石英光催化反应管底部通入恒流量的空气,用300W的氙灯照射一定时间,取样品液体5mL,将其离心分离后,取上层清液,用紫外可见分光光度计测试样品清液在664nm处的吸光度,由于亚甲基蓝的浓度与其吸光度呈一次线性关系,因此最后可通过吸光度来计算亚甲基蓝的降解率。如附图5所示,在该条件下80min的光催化降解率达到96.9%。
以上实施例描述了本发明的基本原理、主要特征及优点,本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明原理的范围下,本发明还会有各种变化和改进,这些变化和改进均落入本发明保护的范围内。
Claims (1)
1.混配型杂多酸有机-无机化合物的制备方法,其特征在于具体步骤为:
步骤S1:将前驱体K5Na4[P2W15 (TaO2) 3]•17H2O 0.2g、NaHSO3 0 .04g及H2O 10mL形成的混合溶液于75℃搅拌30min,再依次向溶液中加入4 ,4´-联吡啶0.06g和CuSO4 0.2g ,然后用1mol/L的盐酸溶液将混合体系的pH值调至2~3,搅拌混合均匀得到混合液;
步骤S2:将步骤S1得到的混合液转移至水热反应釜中,再将该水热反应釜置于可程序控温的烘箱中,设定烘箱的温度参数,1h从室温升温至160℃,于160℃保温72h,然后于48h降温至30℃,最终得到绿色块状晶体即混配型杂多酸有机-无机化合物,产率为54%。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810980354.5A CN109046455B (zh) | 2018-08-27 | 2018-08-27 | 一种混配型杂多酸有机-无机化合物,制备方法及其在可见光催化降解染料废水中的应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810980354.5A CN109046455B (zh) | 2018-08-27 | 2018-08-27 | 一种混配型杂多酸有机-无机化合物,制备方法及其在可见光催化降解染料废水中的应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109046455A CN109046455A (zh) | 2018-12-21 |
CN109046455B true CN109046455B (zh) | 2021-04-13 |
Family
ID=64757040
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810980354.5A Active CN109046455B (zh) | 2018-08-27 | 2018-08-27 | 一种混配型杂多酸有机-无机化合物,制备方法及其在可见光催化降解染料废水中的应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109046455B (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112094185A (zh) * | 2020-08-26 | 2020-12-18 | 河南师范大学 | 一类结构新颖的过渡金属-多酸衍生物及其制备方法 |
CN112897623B (zh) * | 2021-01-21 | 2021-11-30 | 南通大学 | 一种pH响应型印染废水处理剂及其制备方法与应用 |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002146358A (ja) * | 2000-11-17 | 2002-05-22 | Nippon Kayaku Co Ltd | 金属錯体難燃剤 |
CN101379072A (zh) * | 2006-02-07 | 2009-03-04 | 韩国化学研究院 | 多孔有机-无机杂化材料的制备方法 |
CN101927175A (zh) * | 2009-06-26 | 2010-12-29 | 中国科学院福建物质结构研究所 | 一种由Dawson型多酸和六核铜配合物构筑的杂多酸材料及其制备方法和用途 |
CN103566969A (zh) * | 2012-07-31 | 2014-02-12 | 中国科学院大连化学物理研究所 | 一种催化苯羟基化制苯酚的钒基催化材料的制备方法 |
CN104324754A (zh) * | 2014-10-13 | 2015-02-04 | 大连理工大学 | 一类双金属催化光功能性POM/MOFs的制备方法及应用 |
CN104402938A (zh) * | 2014-11-24 | 2015-03-11 | 江苏科技大学 | 一种多酸基镍配合物复合材料及其制备方法与应用 |
CN104815691A (zh) * | 2015-04-17 | 2015-08-05 | 郑州大学 | 具有光催化降解废水中有机污染物的超分子聚合物及其制备方法和应用 |
CN106362796A (zh) * | 2016-05-30 | 2017-02-01 | 河南师范大学 | Ta/W混配型杂多酸,制备方法及其在酸催化和质子导电中的应用 |
CN106391120A (zh) * | 2016-10-31 | 2017-02-15 | 福州大学 | 一种催化降解有机染料的钨氧簇化合物的制备方法及应用 |
CN106905352A (zh) * | 2017-02-28 | 2017-06-30 | 河南省科学院化学研究所有限公司 | 一种铜有机无机杂化化合物及其合成方法 |
CN106948009A (zh) * | 2017-05-24 | 2017-07-14 | 合肥学院 | 一种有机‑无机杂化的钼‑铜类晶体材料及其制备方法 |
-
2018
- 2018-08-27 CN CN201810980354.5A patent/CN109046455B/zh active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002146358A (ja) * | 2000-11-17 | 2002-05-22 | Nippon Kayaku Co Ltd | 金属錯体難燃剤 |
CN101379072A (zh) * | 2006-02-07 | 2009-03-04 | 韩国化学研究院 | 多孔有机-无机杂化材料的制备方法 |
CN101927175A (zh) * | 2009-06-26 | 2010-12-29 | 中国科学院福建物质结构研究所 | 一种由Dawson型多酸和六核铜配合物构筑的杂多酸材料及其制备方法和用途 |
CN103566969A (zh) * | 2012-07-31 | 2014-02-12 | 中国科学院大连化学物理研究所 | 一种催化苯羟基化制苯酚的钒基催化材料的制备方法 |
CN104324754A (zh) * | 2014-10-13 | 2015-02-04 | 大连理工大学 | 一类双金属催化光功能性POM/MOFs的制备方法及应用 |
CN104402938A (zh) * | 2014-11-24 | 2015-03-11 | 江苏科技大学 | 一种多酸基镍配合物复合材料及其制备方法与应用 |
CN104815691A (zh) * | 2015-04-17 | 2015-08-05 | 郑州大学 | 具有光催化降解废水中有机污染物的超分子聚合物及其制备方法和应用 |
CN106362796A (zh) * | 2016-05-30 | 2017-02-01 | 河南师范大学 | Ta/W混配型杂多酸,制备方法及其在酸催化和质子导电中的应用 |
CN106391120A (zh) * | 2016-10-31 | 2017-02-15 | 福州大学 | 一种催化降解有机染料的钨氧簇化合物的制备方法及应用 |
CN106905352A (zh) * | 2017-02-28 | 2017-06-30 | 河南省科学院化学研究所有限公司 | 一种铜有机无机杂化化合物及其合成方法 |
CN106948009A (zh) * | 2017-05-24 | 2017-07-14 | 合肥学院 | 一种有机‑无机杂化的钼‑铜类晶体材料及其制备方法 |
Non-Patent Citations (2)
Title |
---|
"{Ta12}/{Ta16} Cluster-Containing Polytantalotungstates with Remarkable Photocatalytic H2 Evolution Activity";Shujun Li e al.;《Journal of The American Chemical Society》;20121106;第134卷;第19716-19721页 * |
"Grafting Transition Metal–Organic Fragments onto W/Ta Mixed-Addendum Nanoclusters for Broad-Spectrum-Driven Photocatalysis";Tian-Zhan Zhang e al.;《ChemPlusChem》;20140831;第79卷(第8期);第1153-1158页 * |
Also Published As
Publication number | Publication date |
---|---|
CN109046455A (zh) | 2018-12-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109395761B (zh) | 一种氮掺杂BiOIO3光催化剂的制备方法及其应用 | |
CN103240130A (zh) | 光催化分解水用TiO2/MIL-101复合催化剂及制备方法和应用 | |
CN109046455B (zh) | 一种混配型杂多酸有机-无机化合物,制备方法及其在可见光催化降解染料废水中的应用 | |
CN109261172A (zh) | 一种碘氧化铋/溴氧化铋异质结光催化剂的制备方法和用途 | |
CN107684925A (zh) | 一种酸改性g‑C3N4光催化剂及其制备和应用 | |
CN105080553A (zh) | 一种含锡双钙钛矿型光催化降解苯酚催化剂的制备方法 | |
CN110201718B (zh) | 一种红磷/铁基金属有机骨架复合材料的制备及应用 | |
CN104707635A (zh) | 一种高活性磷掺杂钒酸铋光催化剂及其制备方法与应用 | |
CN105268479B (zh) | 基于铁与邻菲罗啉的高效光催化剂的制备方法 | |
CN113578313B (zh) | 一种锰掺杂软铋矿光催化剂及其制备方法和在同步降解六价铬和有机污染物中的应用 | |
CN103447033B (zh) | 一种介孔AgGaO2光催化材料的制备方法 | |
CN104549222A (zh) | 一种可见光催化剂钛酸铬的制备方法及应用 | |
CN102716755B (zh) | 一种具有紫外光催化活性的硫化银/硫化锌复合半导体光催化剂的制备方法 | |
CN104689818A (zh) | 一种ZnO/Ag@AgInO2异质Z型光催化材料及其制备方法 | |
CN110586141A (zh) | 一种用于处理油田废液的Ag-Bi固溶体复合光催化剂的制备方法 | |
CN111518282B (zh) | 可见光催化降解有机染料的羟基吡唑羧酸镉配位聚合物及其制备和应用 | |
CN104998661B (zh) | 可见光光催化剂SnO2/ZnS纳米球复合材料的制备方法 | |
CN112973740B (zh) | 一种生物炭基核壳固体酸催化剂及其制备与应用 | |
CN112076793B (zh) | 基于三元羧酸配体的In-MOF材料及制备方法和应用 | |
CN115254189A (zh) | 一种铁尾矿砂mof复合光催化剂及其制备方法、应用 | |
CN113856766A (zh) | 一种铜席夫碱螯合物插层锌铬水滑石制备方法及其应用 | |
CN108993541B (zh) | 一种光催化剂Cu3VS4的制备方法 | |
CN103861617A (zh) | 铜锌锡硫纳米晶粉末光催化剂的制备方法及应用 | |
CN112973664A (zh) | 一种Aurivillius型含铅层状钙钛矿催化剂、其制备方法及应用 | |
CN111482186B (zh) | 一种处理油田废液有机物的Bi3O4Br光催化剂的制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |