CN111170415A - 一种亚氧化钛/氧化钌复合电极及其制备方法和应用 - Google Patents
一种亚氧化钛/氧化钌复合电极及其制备方法和应用 Download PDFInfo
- Publication number
- CN111170415A CN111170415A CN202010018145.XA CN202010018145A CN111170415A CN 111170415 A CN111170415 A CN 111170415A CN 202010018145 A CN202010018145 A CN 202010018145A CN 111170415 A CN111170415 A CN 111170415A
- Authority
- CN
- China
- Prior art keywords
- titanium
- ruthenium oxide
- composite electrode
- electrode
- roasting
- 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.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001925 ruthenium oxide Inorganic materials 0.000 title claims abstract description 43
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 15
- 239000010936 titanium Substances 0.000 claims abstract description 90
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 89
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 88
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 26
- 239000002071 nanotube Substances 0.000 claims abstract description 23
- 230000003647 oxidation Effects 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 238000004070 electrodeposition Methods 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- 230000010287 polarization Effects 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 12
- 239000002351 wastewater Substances 0.000 claims description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- 239000007853 buffer solution Substances 0.000 claims description 6
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 6
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 6
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 6
- 235000003270 potassium fluoride Nutrition 0.000 claims description 6
- 239000011698 potassium fluoride Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- KELHQGOVULCJSG-UHFFFAOYSA-N n,n-dimethyl-1-(5-methylfuran-2-yl)ethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=C(C)O1 KELHQGOVULCJSG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims 1
- -1 fluoride ions Chemical class 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000007743 anodising Methods 0.000 description 9
- 239000002957 persistent organic pollutant Substances 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- VKRWBTVMYISSEF-UHFFFAOYSA-N oxygen(2-);titanium(2+) Chemical compound [O-2].[Ti+2] VKRWBTVMYISSEF-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
Images
Classifications
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J35/33—Electric or magnetic properties
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
-
- 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
-
- 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
- C02F2305/08—Nanoparticles or nanotubes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
本发明公开了一种亚氧化钛/氧化钌复合电极及其制备方法和应用,它以钛基亚氧化钛纳米管作为底层,掺亚氧化钛氧化钌作为表面复合活性层。将钛基材在含氟离子电解液中进行阳极氧化,取出后加热焙烧,冷却之后再在极化液中进行阴极电化学还原,得到钛基亚氧化钛纳米管;随后将其作为阴极,在掺有亚氧化钛粉末的三氯化钌电解液中进行电沉积,取出后加热焙烧,即得亚氧化钛/氧化钌复合电极。本发明亚氧化钛纳米管在钛基层上生成,直接和钛基材连接,增大了表面积,而且改善了电极的复合表面结构,表面无裂缝产生;并使得亚氧化钛/氧化钌复合活性层分布均匀,充分发挥亚氧化钛与氧化钌的复合结构优势,大大提高了复合电极的使用寿命,同时增强了电催化活性,具有电催化氧化能力强的特点。
Description
技术领域
本发明涉及一种亚氧化钛/氧化钌复合电极及其制备方法和应用,属于电催化氧化电极和电催化氧化处理含有机污染物废水领域。
背景技术
电催化氧化被称为“环境友好”技术,是利用电子作为催化剂,在常温常压下能有效处理含有机污染物废水。随着电催化氧化正在不断的工业化,使得电催化氧化技术应用于大规模的现场应用正在成为可能。电催化氧化中最为关键的就是阳极材料的选择。二氧化钛电催化氧化活性低,直接用于电催化氧化阳极,电催化氧化效率低。亚氧化钛和二氧化钌具有较好的电催化氧化特性,对有机废水的处理具有较好的氧化降解作用。而纳米管由于其独特的结构,较高的有序性,较大的表面积,有助于改善电极的电催化性能。亚氧化钛是不同于二氧化钛或一氧化钛的非化学计量钛氧化物(Ti4O7),但作为阳极材料自身也会被氧化,导致其使用寿命较低。而传统的二氧化钌电极,多采用刷涂制备法,电极表面呈明显“龟裂”状,裂缝多,易导致表面活性涂层的脱落,电极使用寿命不高,电催化氧化能力相对较低。改进电极的组成和复合结构形式,有利于强化提高电极的电催化性能。
发明内容
本发明的目的在于提供一种复合电极,通过改进其复合结构及制备方法优化电极性能,有效提高电极使用寿命和电催化氧化能力。
为了实现上述目的,本发明采取的技术方案如下:
一种亚氧化钛/氧化钌复合电极,它以钛基亚氧化钛纳米管作为底层,掺亚氧化钛氧化钌作为表面复合活性层。
上述亚氧化钛/氧化钌复合电极的制备方法,包括如下步骤:
(1)将钛基材在含氟离子电解液中进行阳极氧化,取出后加热焙烧,冷却之后再在极化液中进行阴极电化学还原,得到钛基亚氧化钛纳米管电极;
(2)将步骤(1)制得的钛基亚氧化钛纳米管电极作为阴极,在掺有亚氧化钛粉末的三氯化钌电解液中进行电沉积,取出后加热焙烧,即得亚氧化钛/氧化钌复合电极。
具体地,步骤(1)中,所述含氟离子电解液为0.05~0.25mol/L氟化钾或氟化钠,和0.08~0.18mol/L硫酸或盐酸的混合溶液;优选为0.15mol/L氟化钾和0.1mol/L硫酸的混合溶液。
步骤(1)中,所述阳极氧化时间为30~120min,电压为20~40V;优选阳极氧化时间为120min,电压为20V。
步骤(1)中,所述的加热焙烧是从室温以1~5℃/min的升温速率,加热到400~550℃,然后保温焙烧2~4小时;优选焙烧温度为500℃,保温焙烧时间3小时,升温速率为2℃/min。
步骤(1)中,所述极化液为含磷酸二氢钾和磷酸氢二钾的pH为6.5~7.5缓冲溶液;优选pH值为7.0;阴极电化学还原时间为2~20min,电流密度为2~20mA/cm2;优选时间为10min,电流密度为10mA/cm2。
具体地,步骤(2)中,所述的电解液中,亚氧化钛的溶度为0.1~2g/L,三氯化钌的溶度为2~20mmol/L,盐酸的溶度为1~10mmol/L;优选亚氧化钛的溶度为1g/L,三氯化钌的溶度为10mmol/L,盐酸的溶度为5mmol/L。
步骤(2)中,所述电沉积时间为20~120min,电流密度为5~25mA/cm2;优选电沉积时间为60min,电流密度为12mA/cm2。
步骤(2)中,所述的加热焙烧是从室温以1~5℃/min的升温速率,加热到450~600℃,然后保温焙烧3~6小时;优选焙烧温度为550℃,保温焙烧时间5小时,升温速率为3℃/min。
本发明进一步提供上述亚氧化钛/氧化钌复合电极在处理含有机污染物废水中作为电催化氧化阳极的应用。
有益效果:
(1)本发明制备方法具有易于控制、设备要求低、成本较低等特点。
(2)通过本发明方法制备复合电极,亚氧化钛纳米管在钛基层上生成,直接和钛基材连接,增大了表面积,而且改善了电极的复合表面结构,表面致密、无裂缝;并使得亚氧化钛/氧化钌复合活性层分布均匀,充分发挥亚氧化钛与氧化钌的复合结构优势,大大提高了复合电极的使用寿命,同时增强了电催化活性,具有电催化氧化能力强的特点。
附图说明
下面结合附图和具体实施方式对本发明做更进一步的具体说明,本发明的上述和/或其他方面的优点将会变得更加清楚。
图1为实施例1亚氧化钛纳米管电极表面扫描电镜SEM图。
图2为实施例1亚氧化钛/氧化钌复合电极表面扫描电镜SEM图。
图3为实施例1亚氧化钛/氧化钌复合电极表面能谱分析EDS图。
具体实施方式
根据下述实施例,可以更好地理解本发明。
实施例1
一种亚氧化钛/氧化钌复合电极,具体制备如下:将钛基材在0.15mol/L氟化钾和0.1mol/L硫酸的电解液溶液中进行阳极氧化,阳极氧化时间为120min,电压为20V,取出后加热焙烧,设定焙烧温度为500℃,焙烧时间3小时,升温速率为2℃/min;冷却至室温之后再在含磷酸二氢钾和磷酸氢二钾的pH为7.0缓冲溶液中进行阴极电化学还原,控制还原时间为10min,电流密度为10mA/cm2,得到钛基亚氧化钛纳米管电极,电极表面电镜图如图1所示,可以看出,纳米管结构规整,分布均匀,纳米管的直径达到80~110nm,由于其纳米管是二维结构,有效提高了钛板底层结构的表面积;将制得的钛基亚氧化钛纳米管电极作为阴极,在溶度为1g/L亚氧化钛,10mmol/L三氯化钌和5mmol/L盐酸的电解液中进行电沉积,控制电沉积时间为60min,电流密度为12mA/cm2;取出后加热焙烧,设定焙烧温度为550℃,焙烧时间5小时,升温速率为3℃/min,制得亚氧化钛/氧化钌复合电极。亚氧化钛/氧化钌复合电极的扫描电镜图如图2所示,可以明显看出电极表面致密、无裂缝,亚氧化钛/氧化钌复合晶粒细小、密集,并且分布均匀,可充分发挥亚氧化钛与氧化钌的复合结构优势,有效提高电极使用寿命和电催化氧化能力。电极的能谱图如图3所示,检测出了电极的O,Ru和Ti元素成分。在1A/cm2的电流密度条件下进行电极的强化加速寿命测试,得出亚氧化钛/氧化钌复合电极的加速使用寿命高达63h。亚氧化钛/氧化钌复合电极用于处理工业园区废水(有机污染物即COD为175mg/L),调节电流密度为15mA/cm2,作为阳极电催化氧化反应1.5小时,COD去除率达到82%。
实施例2
一种亚氧化钛/氧化钌复合电极,具体制备如下:将钛基材在0.05mol/L氟化钠和0.08mol/L硫酸的电解液溶液中进行阳极氧化,阳极氧化时间为30min,电压为40V,取出后加热焙烧,设定焙烧温度为400℃,焙烧时间4小时,升温速率为1℃/min;冷却至室温之后再在含磷酸二氢钾和磷酸氢二钾的pH为6.5缓冲溶液中进行阴极电化学还原,控制还原时间为2min,电流密度为20mA/cm2,得到钛基亚氧化钛纳米管电极;将制得的钛基亚氧化钛纳米管电极作为阴极,在溶度为2g/L亚氧化钛,20mmol/L三氯化钌和10mmol/L盐酸的电解液中进行电沉积,控制电沉积时间为20min,电流密度为5mA/cm2;取出后加热焙烧,设定焙烧温度为450℃,焙烧时间6小时,升温速率为1℃/min,制得亚氧化钛/氧化钌复合电极。在1A/cm2的电流密度条件下进行电极的强化加速寿命测试,得出亚氧化钛/氧化钌复合电极的加速使用寿命高达60h。亚氧化钛/氧化钌复合电极用于处理工业园区废水(COD为175mg/L),调节电流密度为15mA/cm2,作为阳极电催化氧化反应1.5小时,COD去除率达到83%。
实施例3
一种亚氧化钛/氧化钌复合电极,具体制备如下:将钛基材在0.25mol/L氟化钾和0.18mol/L硫酸的电解液溶液中进行阳极氧化,阳极氧化时间为60min,电压为25V,取出后加热焙烧,设定焙烧温度为550℃,焙烧时间2小时,升温速率为5℃/min;冷却至室温之后再在含磷酸二氢钾和磷酸氢二钾的pH为7.5缓冲溶液中进行阴极电化学还原,控制还原时间为20min,电流密度为2mA/cm2,得到钛基亚氧化钛纳米管电极;将制得的钛基亚氧化钛纳米管电极作为阴极,在溶度为0.1g/L亚氧化钛,2mmol/L三氯化钌和1mmol/L盐酸的电解液中进行电沉积,控制电沉积时间为120min,电流密度为20mA/cm2;取出后加热焙烧,设定焙烧温度为600℃,焙烧时间3小时,升温速率为5℃/min,制得亚氧化钛/氧化钌复合电极。在1A/cm2的电流密度条件下进行电极的强化加速寿命测试,得出亚氧化钛/氧化钌复合电极的加速使用寿命高达58h。亚氧化钛/氧化钌复合电极用于处理工业园区废水(COD为175mg/L),调节电流密度为15mA/cm2,作为阳极电催化氧化反应1.5小时,COD去除率达到80%。
对比例1
一种亚氧化钛电极,具体制备如下:将钛基材在0.15mol/L氟化钠和0.1mol/L硫酸的电解液溶液中进行阳极氧化,阳极氧化时间为90min,电压为22V,取出后加热焙烧,设定焙烧温度为500℃,焙烧时间3小时,升温速率为2℃/min;冷却至室温之后再在含磷酸二氢钾和磷酸氢二钾的pH为7.0缓冲溶液中进行阴极电化学还原,控制还原时间为10min,电流密度为10mA/cm2,制得钛基亚氧化钛纳米管电极。在1A/cm2的电流密度条件下进行电极的强化加速寿命测试,得出亚氧化钛电极的加速使用寿命仅为2h。亚氧化钛电极用于处理工业园区废水(有机污染物即COD为175mg/L),调节电流密度为15mA/cm2,作为阳极电催化氧化反应1.5小时,COD去除率为67%。
对比例2
一种氧化钌复合电极,具体制备如下:将钛基材在0.15mol/L氟化钾和0.1mol/L硫酸的电解液溶液中进行阳极氧化,阳极氧化时间为90min,电压为25V,取出后加热焙烧,设定焙烧温度为500℃,焙烧时间3小时,升温速率为2℃/min;即得到钛基二氧化钛纳米管电极;将制得的钛基二氧化钛纳米管电极作为阴极,在溶度为10mmol/L三氯化钌和5mmol/L盐酸的电解液中进行电沉积,控制电沉积时间为60min,电流密度为12mA/cm2;取出后加热焙烧,设定焙烧温度为550℃,焙烧时间5小时,升温速率为3℃/min,制得氧化钌复合电极。在1A/cm2的电流密度条件下进行电极的强化加速寿命测试,得出氧化钌电极的加速使用寿命为32h。氧化钌复合电极用于处理工业园区废水(有机污染物即COD为175mg/L),调节电流密度为15mA/cm2,作为阳极电催化氧化反应1.5小时,COD去除率仅55%。
本发明提供了一种亚氧化钛/氧化钌复合电极及其制备方法和应用的思路及方法,具体实现该技术方案的方法和途径很多,以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。本实施例中未明确的各组成部分均可用现有技术加以实现。
Claims (10)
1.一种亚氧化钛/氧化钌复合电极,其特征在于,它以钛基亚氧化钛纳米管作为底层,掺亚氧化钛氧化钌作为表面复合活性层。
2.权利要求1所述亚氧化钛/氧化钌复合电极的制备方法,其特征在于,包括如下步骤:
(1)将钛基材在含氟离子电解液中进行阳极氧化,取出后加热焙烧,冷却之后再在极化液中进行阴极电化学还原,得到钛基亚氧化钛纳米管电极;
(2)将步骤(1)制得的钛基亚氧化钛纳米管电极作为阴极,在掺有亚氧化钛粉末的三氯化钌电解液中进行电沉积,取出后加热焙烧,即得亚氧化钛/氧化钌复合电极。
3.根据权利要求2所述的制备方法,其特征在于,步骤(1)中,所述含氟离子电解液为0.05~0.25mol/L氟化钾或氟化钠,和0.08~0.18mol/L硫酸或盐酸的混合溶液。
4.根据权利要求2所述的制备方法,其特征在于,步骤(1)中,所述阳极氧化时间为30~120min,电压为20~40V。
5.根据权利要求2所述的制备方法,其特征在于,步骤(1)中,所述的加热焙烧是从室温以1~5℃/min的升温速率,加热到400~550℃,然后保温焙烧2~4小时。
6.根据权利要求2所述的制备方法,其特征在于,步骤(1)中,所述极化液为含磷酸二氢钾和磷酸氢二钾的pH为6.5~7.5缓冲溶液;阴极电化学还原时间为2~20min,电流密度为2~20mA/cm2。
7.根据权利要求2所述的制备方法,其特征在于,步骤(2)中,所述的电解液中,亚氧化钛的溶度为0.1~2g/L,三氯化钌的溶度为2~20mmol/L,盐酸的溶度为1~10mmol/L。
8.根据权利要求2所述的制备方法,其特征在于,步骤(2)中,所述电沉积时间为20~120min,电流密度为5~25mA/cm2。
9.根据权利要求2所述的制备方法,其特征在于,步骤(2)中,所述的加热焙烧是从室温以1~5℃/min的升温速率,加热到450~600℃,然后保温焙烧3~6小时。
10.权利要求1所述亚氧化钛/氧化钌复合电极在处理含有机污染物废水中作为电催化氧化阳极的应用。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010018145.XA CN111170415B (zh) | 2020-01-08 | 2020-01-08 | 一种亚氧化钛/氧化钌复合电极及其制备方法和应用 |
US16/816,203 US11519088B2 (en) | 2020-01-08 | 2020-03-11 | Titanium sub-oxide/ruthenium oxide composite electrode and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010018145.XA CN111170415B (zh) | 2020-01-08 | 2020-01-08 | 一种亚氧化钛/氧化钌复合电极及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111170415A true CN111170415A (zh) | 2020-05-19 |
CN111170415B CN111170415B (zh) | 2020-10-09 |
Family
ID=70654544
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010018145.XA Active CN111170415B (zh) | 2020-01-08 | 2020-01-08 | 一种亚氧化钛/氧化钌复合电极及其制备方法和应用 |
Country Status (2)
Country | Link |
---|---|
US (1) | US11519088B2 (zh) |
CN (1) | CN111170415B (zh) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112250145A (zh) * | 2020-10-30 | 2021-01-22 | 南京理工大学 | 一种多孔钛基亚氧化钛纳米管二氧化铅电极的制备与应用 |
CN113003669A (zh) * | 2021-02-25 | 2021-06-22 | 哈尔滨工业大学 | 一种用于电催化氧化废水处理的氟修饰亚氧化钛活性膜电极的制备方法及穿流式水处理模式 |
CN113546526A (zh) * | 2021-08-30 | 2021-10-26 | 大连海事大学 | 非对称中空纤维钛基膜及其制备方法 |
CN113603191A (zh) * | 2021-08-23 | 2021-11-05 | 中国科学院生态环境研究中心 | 一种金属钌基电极及其制备方法和应用 |
CN114229964A (zh) * | 2021-11-23 | 2022-03-25 | 东莞理工学院 | 一种以Ti4O7为基底的表面刻蚀和氟化的阳极制备方法及应用 |
CN114249394A (zh) * | 2021-12-24 | 2022-03-29 | 盐城工学院 | 一种掺锡锑的亚氧化钛中间层微孔二氧化钌电极的制备方法 |
CN115466986A (zh) * | 2022-09-28 | 2022-12-13 | 西南石油大学 | 一种用于废水电解制氢的电极及其制备方法和应用 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114438553A (zh) * | 2022-02-09 | 2022-05-06 | 宝鸡钛普锐斯钛阳极科技有限公司 | 一种钛基IrO2-TaO5涂层阳极底层的制备方法 |
CN114457376B (zh) * | 2022-02-18 | 2023-08-04 | 北京工业大学 | 一种电化学氮还原用硼掺杂二氧化钛纳米管阵列固载二硫化钼的制备方法 |
CN115140808B (zh) * | 2022-07-01 | 2023-10-03 | 西部金属材料股份有限公司 | 一种复合阳极材料及其制备方法和应用 |
CN115925056B (zh) * | 2022-12-15 | 2024-04-16 | 华中师范大学 | 一种磷掺杂亚氧化钛/泡沫钛电极的制备及其用于处理重金属废水的方法 |
CN115818796B (zh) * | 2023-01-10 | 2024-05-24 | 东莞理工学院 | 一种Zr金属原子掺杂Ti4O7复合电极的制备及其使用方法 |
CN116161752A (zh) * | 2023-03-09 | 2023-05-26 | 东莞理工学院 | 一种复合电极的制备方法及其在含硝酸盐废水中的应用 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0047595A1 (en) * | 1980-09-10 | 1982-03-17 | Marston Palmer Ltd. | Electrochemical cell |
US20030085199A1 (en) * | 2001-11-08 | 2003-05-08 | Korea Atomic Energy Research Institute & Technology Winners Co., Ltd. | Method for manufacturing catalytic oxide anode using high temperature sintering |
US20040211458A1 (en) * | 2003-04-28 | 2004-10-28 | General Electric Company | Tandem photovoltaic cell stacks |
CN101423270A (zh) * | 2008-10-09 | 2009-05-06 | *** | 一种高效电催化高级氧化技术电极材料 |
CN103395865A (zh) * | 2013-07-30 | 2013-11-20 | 南京理工大学 | 钛基管式二氧化钌涂层膜电极及其制备方法 |
CN104016673A (zh) * | 2014-05-28 | 2014-09-03 | 长沙沃瑞新材料科技有限公司 | 一种亚氧化钛导电陶瓷电极的制备工艺 |
CN104032355A (zh) * | 2014-06-20 | 2014-09-10 | 中南大学 | 半金属态导电亚氧化钛纳米管阵列的制备方法 |
CN104591342A (zh) * | 2014-11-10 | 2015-05-06 | 牛军峰 | 用于污水深度处理的Ti/Ebonex/PbO2电极的制备方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101857288B (zh) * | 2010-06-18 | 2011-10-26 | 南京理工大学 | 钛基二氧化钛纳米管二氧化锡电极的制备方法 |
CN105070943B (zh) * | 2015-08-27 | 2018-03-30 | 深圳市鑫峰昌技术股份有限公司 | 一种快速充电锂电池 |
-
2020
- 2020-01-08 CN CN202010018145.XA patent/CN111170415B/zh active Active
- 2020-03-11 US US16/816,203 patent/US11519088B2/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0047595A1 (en) * | 1980-09-10 | 1982-03-17 | Marston Palmer Ltd. | Electrochemical cell |
US20030085199A1 (en) * | 2001-11-08 | 2003-05-08 | Korea Atomic Energy Research Institute & Technology Winners Co., Ltd. | Method for manufacturing catalytic oxide anode using high temperature sintering |
US20040211458A1 (en) * | 2003-04-28 | 2004-10-28 | General Electric Company | Tandem photovoltaic cell stacks |
CN101423270A (zh) * | 2008-10-09 | 2009-05-06 | *** | 一种高效电催化高级氧化技术电极材料 |
CN103395865A (zh) * | 2013-07-30 | 2013-11-20 | 南京理工大学 | 钛基管式二氧化钌涂层膜电极及其制备方法 |
CN104016673A (zh) * | 2014-05-28 | 2014-09-03 | 长沙沃瑞新材料科技有限公司 | 一种亚氧化钛导电陶瓷电极的制备工艺 |
CN104032355A (zh) * | 2014-06-20 | 2014-09-10 | 中南大学 | 半金属态导电亚氧化钛纳米管阵列的制备方法 |
CN104591342A (zh) * | 2014-11-10 | 2015-05-06 | 牛军峰 | 用于污水深度处理的Ti/Ebonex/PbO2电极的制备方法 |
Non-Patent Citations (3)
Title |
---|
北京市《金属切削理论与实践》编委会: "《电解加工》", 31 October 1981, 北京出版社 * |
王文兵等: "钛基金属氧化物涂层电极的研究进展", 《电镀与涂饰》 * |
胡忠心等: "新型纳米二氧化铅电极电催化性能研究", 《中国科技论文在线》 * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112250145A (zh) * | 2020-10-30 | 2021-01-22 | 南京理工大学 | 一种多孔钛基亚氧化钛纳米管二氧化铅电极的制备与应用 |
CN112250145B (zh) * | 2020-10-30 | 2021-11-30 | 南京理工大学 | 一种多孔钛基亚氧化钛纳米管二氧化铅电极的制备与应用 |
CN113003669A (zh) * | 2021-02-25 | 2021-06-22 | 哈尔滨工业大学 | 一种用于电催化氧化废水处理的氟修饰亚氧化钛活性膜电极的制备方法及穿流式水处理模式 |
CN113003669B (zh) * | 2021-02-25 | 2022-06-28 | 哈尔滨工业大学 | 一种用于电催化氧化废水处理的氟修饰亚氧化钛活性膜电极的制备方法及穿流式水处理模式 |
CN113603191A (zh) * | 2021-08-23 | 2021-11-05 | 中国科学院生态环境研究中心 | 一种金属钌基电极及其制备方法和应用 |
CN113546526A (zh) * | 2021-08-30 | 2021-10-26 | 大连海事大学 | 非对称中空纤维钛基膜及其制备方法 |
CN113546526B (zh) * | 2021-08-30 | 2022-07-05 | 大连海事大学 | 非对称中空纤维钛基膜及其制备方法 |
CN114229964A (zh) * | 2021-11-23 | 2022-03-25 | 东莞理工学院 | 一种以Ti4O7为基底的表面刻蚀和氟化的阳极制备方法及应用 |
CN114249394A (zh) * | 2021-12-24 | 2022-03-29 | 盐城工学院 | 一种掺锡锑的亚氧化钛中间层微孔二氧化钌电极的制备方法 |
CN115466986A (zh) * | 2022-09-28 | 2022-12-13 | 西南石油大学 | 一种用于废水电解制氢的电极及其制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
US20200208282A1 (en) | 2020-07-02 |
CN111170415B (zh) | 2020-10-09 |
US11519088B2 (en) | 2022-12-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111170415B (zh) | 一种亚氧化钛/氧化钌复合电极及其制备方法和应用 | |
CN101857288B (zh) | 钛基二氧化钛纳米管二氧化锡电极的制备方法 | |
CN112647086B (zh) | 一种用于pem水电解池的钛纤维毡阳极扩散层及其制备方法与应用 | |
US8946116B2 (en) | Nanometer powder catalyst and its preparation method | |
JP4280346B2 (ja) | ガス拡散電極用触媒 | |
JP4673628B2 (ja) | 水素発生用陰極 | |
JP4341838B2 (ja) | 電解用陰極 | |
CN113061926A (zh) | 一种用于pem水电解池的亚氧化钛阳极扩散层及其制备方法与应用 | |
JPH06330367A (ja) | ガス電極の製造方法 | |
JP4290454B2 (ja) | ガス拡散電極の製造方法、電解槽及び電解方法 | |
KR102055597B1 (ko) | 고체 산화물 멤브레인용 복합체, 이의 제조방법 및 이를 포함하는 고체 산화물 멤브레인 | |
CN106591915A (zh) | 一种具有三层结构的等离子体电解氧化催化膜及其制备方法 | |
CN113430539B (zh) | 使用电解***电解还原二氧化碳时提高二氧化碳转化率的方法 | |
CN114272920A (zh) | 一种有机污染物降解用复合氧化物涂层电极及其制备方法 | |
CN110065932B (zh) | 一种锂***式硒类化合物、其制备方法及应用 | |
CN109205738B (zh) | 锡锑-碳气凝胶复合吸附性电极及其制备方法 | |
CN108585126B (zh) | 一种过氧化铅电极及其制备方法和应用 | |
CN111732159A (zh) | 一种新型光电催化反应器及其构建方法和应用及空气扩散阴极的应用 | |
JPH0417689A (ja) | 水電解用電極及びその製造方法 | |
CN115650376B (zh) | 一种基于酚醛树脂辅助的dsa电极及其制备方法与应用 | |
CN111943327A (zh) | 用于酸性废水处理的具有RuO2-IrO2中间层的电极材料及制备方法 | |
CN110217861B (zh) | 一种长寿命多孔钛基二氧化铅电极材料的制备及应用 | |
CN114959771B (zh) | 一种镍基电催化剂及产氢协同降解甲醛废水电解池 | |
CN113308727B (zh) | 二氧化钛纳米管、基于二氧化钛纳米管的复合电极、及其制备方法、应用 | |
KR890001132B1 (ko) | 산소발생용 양극 및 그의 제조방법 |
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 |