CN108821394A - 一种钼酸铁(ii)/氧化石墨烯催化电极的制备方法 - Google Patents

一种钼酸铁(ii)/氧化石墨烯催化电极的制备方法 Download PDF

Info

Publication number
CN108821394A
CN108821394A CN201810675205.8A CN201810675205A CN108821394A CN 108821394 A CN108821394 A CN 108821394A CN 201810675205 A CN201810675205 A CN 201810675205A CN 108821394 A CN108821394 A CN 108821394A
Authority
CN
China
Prior art keywords
preparation
electrode
mixed solution
catalysis
graphene oxide
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
Application number
CN201810675205.8A
Other languages
English (en)
Other versions
CN108821394B (zh
Inventor
柳丽芬
唐丽娜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian University of Technology
Original Assignee
Dalian University of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dalian University of Technology filed Critical Dalian University of Technology
Priority to CN201810675205.8A priority Critical patent/CN108821394B/zh
Publication of CN108821394A publication Critical patent/CN108821394A/zh
Application granted granted Critical
Publication of CN108821394B publication Critical patent/CN108821394B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • 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
    • C02F2001/46152—Electrodes characterised by the shape or form
    • 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
    • C02F2305/10—Photocatalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

本发明提供了一种钼酸铁(II)/氧化石墨烯催化电极的制备方法，属于水解制氢、污水净化材料与废水资源化与能源化利用技术领域，涉及应用一步水热合成法，在导电基底上制备负载钼酸铁(II)/氧化石墨烯的催化电极。在碳纤维布表面原位水热合成制备复合氧化石墨烯及钼酸铁(II)廉价高性能光电催化剂及催化导电双功能膜电极。此方法制备的双功能膜电极具有良好的催化导电性能。该功能膜可同时用作电化学体系的工作电极和光催化反应的催化材料。本发明的效果和益处是该法制备的廉价催化剂及导电催化双功能膜电极，具有高效降解持久性有机污染物及同时产生清洁能源物质氢气的性能，实现废水的资源化与能源化。

Description

一种钼酸铁(II)/氧化石墨烯催化电极的制备方法
技术领域
本发明属于污水净化与废水资源化、能源化利用技术领域，涉及应用一步水热合成法制备负载型钼酸铁(II)/氧化石墨烯的催化电极。以碳纤维布作为基底，原位生长制备催化导电双功能膜电极。通过光电催化(PEC)技术降解污水中持久性有机物，同时进行能源化产氢的操作。
背景技术
光电催化技术(Photoelectrocatalysis method，简称PEC)是一种融合了电化学和光催化的新型电化学高级氧化技术。催化电极吸收光子后，就会在其表面形成光生电子-空穴对，光生载流子彼此分离并迁移到催化电极表面后会对体系中相应物质进行氧化还原反应。但光催化反应存在的主要问题是光生载流子极易复合，降低氧化还原效率。此时，在其表面施加一定的偏压，就会增加光生载流子的分离效率，大大增强体系的氧化还原效率。因此，该技术的核心是通过选择半导体光电极(或粉末)材料和(或)改变电极的表面状态(表面处理或表面修饰催化剂)来加速体系的氧化还原反应。
将电化学及光催化技术进行耦合，充分利用各自优势，相互协同，创造污水有机物处理+水分解产氢的资源化、能源化模式。目前应用的催化电极多为贵金属材料，成本高昂。钼酸铁(II)作为一种生产成本低廉的催化剂，催化性能优异，性价比高，稳定性好，目前仍无研究者将此方法应用于催化电极的制备。
发明内容
本发明的目的是提供一种催化导电双功能膜电极的制备方法，解决了光催化降解中光生载流子极易复合，氧化还原效率低的问题；在光电催化降解过程中，同步去除持久性有机污染物和水分解产氢。
本发明的技术方案：
一种钼酸铁(II)/氧化石墨烯催化电极的制备方法，步骤如下：
1)将氯化亚铁FeCl2·4H2O与硫脲按摩尔比0.2～1：1溶于去离子水中，充分搅拌，得到澄清透明的混合溶液a；
2)称取一定质量的钼酸铵(NH4)6Mo7O24·4H2O，将其加入到上述混合溶液a中，充分搅拌后，得到混合溶液b；钼酸铵与硫脲的摩尔比为0.2：1；
3)将一定质量的氧化石墨烯加入到混合溶液b中，充分搅拌，得到混合溶液c；氧化石墨烯与硫脲的质量比为7～30×10-3：1；
4)将碳纤维布卷曲放入高压密闭反应器中，然后将混合溶液c倒入该高压密闭反应器，密封高压密闭反应器；
5)将高压密闭反应器在120℃～240℃下恒温6～24h，取出，自然冷却；
6)取出制备的催化导电膜，去离子水冲洗干净后，晾干备用。
本发明的有益效果：制备出的廉价催化导电双功能膜电极能够显著提高光电催化反应效果；在光电催化降解持久性有机污染物的同时，可分解水产氢；既可提高废水资源化转化效率，又可提高废水能源化转化效率。
附图说明
图1是功能膜电极X射线衍射(XRD)图。
图中：横坐标表示衍射角度(2θ)，单位°，纵坐标表示相对强度。
图2是双功能膜电极扫描电子显微镜(SEM)图。
图3是双功能膜电极透射电子显微镜(TEM)图。
图4是双功能膜电极光电催化降解持久性有机污染物图。
图中：横坐标表示时间，单位min，纵坐标表示水样吸光度和去除效率，单位无和％，方块、三角分别表示水样吸光度、去除效率。
具体实施方式
以下结合技术方案和附图详细叙述本发明的具体实施方式。
将4.98g氯化亚铁FeCl2·4H2O与1.90g硫脲溶于50ml去离子水中，充分搅拌，得到澄清透明的混合溶液；将6.18g钼酸铵(NH4)6Mo7O24·4H2O，加入到上述混合溶液，充分搅拌；将20ml自制2.83g/L氧化石墨烯加入到上述混合溶液中，搅拌均匀；将7cm×12cm碳纤维布卷曲贴壁放入高压反应釜聚四氟乙烯内衬中，然后将上述混合溶液倒入该反应釜，密封反应釜；将反应釜在180℃下恒温12h，取出，自然冷却；取出制备的催化导电膜电极，去离子水冲洗干净后，晾干备用。
X射线衍射图：制备的催化导电膜电极的主要成分为单斜相β-FeMoO4，与JCPDS卡No.22-0628相匹配。
扫描电子显微镜与透射电子显微镜：钼酸铁(II)/氧化石墨烯催化导电膜电极由粒径尺寸分布在70-160nm的纳米片堆积在炭纤维布表面形成。
功能膜催化性能检验：功能膜电极作为阴极，铂片为阳极，在300W氙灯、恒电流模式下，加压进行光电催化降解10mg/L黄连素的性能测试。

Claims (1)

1.一种钼酸铁(II)/氧化石墨烯催化电极的制备方法，其特征在于，步骤如下：
1)将氯化亚铁FeCl2·4H2O与硫脲按摩尔比0.2～1：1溶于去离子水中，充分搅拌，得到澄清透明的混合溶液a；
2)称取一定质量的钼酸铵(NH4)6Mo7O24·4H2O，将其加入到上述混合溶液a中，充分搅拌后，得到混合溶液b；钼酸铵与硫脲的摩尔比为0.2：1；
3)将一定质量的氧化石墨烯加入到混合溶液b中，充分搅拌，得到混合溶液c；氧化石墨烯与硫脲的质量比为7～30×10-3：1；
4)将碳纤维布卷曲放入高压密闭反应器中，然后将混合溶液c倒入该高压密闭反应器，密封高压密闭反应器；
5)将高压密闭反应器在120℃～240℃下恒温6～24h，取出，自然冷却；
6)取出制备的催化导电膜，去离子水冲洗干净后，晾干备用。
CN201810675205.8A 2018-06-27 2018-06-27 一种钼酸铁(ii)/氧化石墨烯催化电极的制备方法 Active CN108821394B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810675205.8A CN108821394B (zh) 2018-06-27 2018-06-27 一种钼酸铁(ii)/氧化石墨烯催化电极的制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810675205.8A CN108821394B (zh) 2018-06-27 2018-06-27 一种钼酸铁(ii)/氧化石墨烯催化电极的制备方法

Publications (2)

Publication Number Publication Date
CN108821394A true CN108821394A (zh) 2018-11-16
CN108821394B CN108821394B (zh) 2021-10-15

Family

ID=64138759

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810675205.8A Active CN108821394B (zh) 2018-06-27 2018-06-27 一种钼酸铁(ii)/氧化石墨烯催化电极的制备方法

Country Status (1)

Country Link
CN (1) CN108821394B (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110498485A (zh) * 2019-08-28 2019-11-26 东莞理工学院 高效钛基钼酸亚铁电极的制备方法及应用
CN113816432A (zh) * 2021-09-06 2021-12-21 广东工业大学 一种纳米片自组装球状钼酸亚铁材料及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104319102A (zh) * 2014-10-23 2015-01-28 上海工程技术大学 一种制备负载三维花状石墨烯/二硫化钼复合材料的纤维状对电极的方法
CN107663637A (zh) * 2017-09-05 2018-02-06 中国科学院福建物质结构研究所 钼酸盐纳米复合材料及其制备方法和应用

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104319102A (zh) * 2014-10-23 2015-01-28 上海工程技术大学 一种制备负载三维花状石墨烯/二硫化钼复合材料的纤维状对电极的方法
CN107663637A (zh) * 2017-09-05 2018-02-06 中国科学院福建物质结构研究所 钼酸盐纳米复合材料及其制备方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUNDAN LIU,LONG REN,XIANG QI,YAO WANG,XUEJUN LIU,JIANXIN ZHONG: "One-step hydrothermal fabrication and enhancement of the photocatalytic performance of CdMoO4/CdS hybrid materials", 《RSC ADVANCES》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110498485A (zh) * 2019-08-28 2019-11-26 东莞理工学院 高效钛基钼酸亚铁电极的制备方法及应用
CN110498485B (zh) * 2019-08-28 2022-05-10 东莞理工学院 高效钛基钼酸亚铁电极的制备方法及应用
CN113816432A (zh) * 2021-09-06 2021-12-21 广东工业大学 一种纳米片自组装球状钼酸亚铁材料及其制备方法和应用

Also Published As

Publication number Publication date
CN108821394B (zh) 2021-10-15

Similar Documents

Publication Publication Date Title
Yuan et al. Enhanced photocatalytic H 2 evolution over noble-metal-free NiS cocatalyst modified CdS nanorods/gC 3 N 4 heterojunctions
Yu et al. Microwave-assisted hydrothermal synthesis of Sn3O4 nanosheet/rGO planar heterostructure for efficient photocatalytic hydrogen generation
CN106435635B (zh) 一种高效光电催化分解水产氧电极的制备方法及应用
Xu et al. Synthesis and behaviors of g-C3N4 coupled with LaxCo3-xO4 nanocomposite for improved photocatalytic activeity and stability under visible light
CN108499585B (zh) 含磷复合物及其制备与应用
Yu et al. Cd0. 5Zn0. 5S/Ni2P noble-metal-free photocatalyst for high-efficient photocatalytic hydrogen production: Ni2P boosting separation of photocarriers
Hao et al. Modulating photogenerated electron transfer with selectively exposed Co–Mo facets on a novel amorphous gC 3 N 4/Co x Mo 1− x S 2 photocatalyst
Yu et al. 2D CdS functionalized by NiS2-doped carbon nanosheets for photocatalytic H2 evolution
Li et al. Nanoflower-like Ti3CN@ TiO2/CdS heterojunction photocatalyst for efficient photocatalytic water splitting
CN106987857A (zh) 单层金属结构二硫化钼/氧化还原石墨烯复合物及其制备方法
Chen et al. Non-noble metal Co as active sites on TiO2 nanorod for promoting photocatalytic H2 production
CN111348728B (zh) 一种MOF和HrGO共修饰的钒酸铋电极及其制备方法和应用
Li et al. ZIF-67 derived Co@ NC/g-C3N4 as a photocatalyst for enhanced water splitting H2 evolution
Wang et al. The g-C3N4 nanosheets decorated by plasmonic Au nanoparticles: A heterogeneous electrocatalyst for oxygen evolution reaction enhanced by sunlight illumination
Jin et al. A facile approach to fabricating carbonaceous material/g-C3N4 composites with superior photocatalytic activity
WO2019085532A1 (zh) 一种三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料及其制备方法
Liu et al. Enhancing photocatalytic nitrogen fixation performance of Co-doped bismuth molybdate through band engineering tuning
Tang et al. The construction and performance of photocatalytic-fuel-cell with Fe-MoS2/reduced graphene oxide@ carbon fiber cloth and ZnFe2O4/Ag/Ag3VO4@ carbon felt as photo electrodes
Kong et al. Synthesis and photocatalytic hydrogen activity of Mo1− xS2 nanosheets with controllable Mo vacancies
Ji et al. Construction of 3D leaf-like Bi2O3-Bi2S3 nanosheets on Fe2O3 nanofilms and its photoelectrocatalytic performance
Yang et al. Ascorbic acid-assisted hydrothermal route to create mesopores in polymeric carbon nitride for increased photocatalytic hydrogen generation
CN106076312B (zh) 一种Nb(OH)5纳米线/还原氧化石墨烯复合光催化剂及其制备方法与应用
CN108821394A (zh) 一种钼酸铁(ii)/氧化石墨烯催化电极的制备方法
Chen et al. Microwave-assisted synthesis of organic–inorganic hybrid porous g-C3N4/CdS–diethylenetriamine S-scheme heterojunctions with enhanced visible light hydrogen production
Guo et al. WS 2/In 2 S 3 composite photocatalyst for photocatalytic H 2 generation and pollutant degradation

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