Investigation of nitrate removal in water by CuO-Co3O4 modified titanium-based nanoelectrode

doi:10.19965/j.cnki.iwt.2024-0068

Abstract

Abstract:

In this study, a CuO-Co₃O₄ modified titanium-based nanoelectrode(CuO-Co₃O₄@TBNE) was synthesized by two hydrothermal and calcination methods based on the metal organic framework(MOF) synthesis route. XRD and XPS characterization indicated that the electrode surface was composed of Co₃O₄ and Cu²⁺. SEM and EDS characterization revealed that Cu element with a mass fraction of approximately 7.85% was loaded onto Co₃O₄ nanorods. The electrocatalytic reduction ability of the electrode for NO₃ ^--N in water was tested using linear sweep voltammetry, and was found to have high current response density and exhibit strong electrochemical activity. It was used for electrocatalytic reduction to remove nitrate from water. The results showed that under the conditions of pH=7, current density of 10 mA/cm², and initial mass concentration of NO₃ ^--N 50 mg/L, the removal rate of NO₃ ^--N reached 99.73% after electrolysis for 2 hours. The electrode could work in a wide range of acidity and alkalinity, and the electrochemical reduction effect was better under neutral and acidic conditions than under alkaline conditions. In addition, when adding Cl^- with a mass concentration of 1 000 mg/L, the total nitrogen removal rate of 93.7% could be achieved. The hydrogen atom radical scavenging experiment using tertiary butanol(TBA) showed that the reduction of NO₃ ^--N by the electrode catalytic system mainly followed the direct electron reduction pathway. The CuO-Co₃O₄@TBNE electrode showed good stability and extremely low metal leaching in 10 cycles.

Key words: tricobalt tetraoxide, titanium-based nanoelectrode, nitrate, electrocatalysis, metal-organic frameworks

摘要：

依据金属有机框架（MOF）合成路径，经两次水热再煅烧的方法制备CuO-Co₃O₄改性钛基纳米电极（CuO-Co₃O₄@TBNE）。XRD和XPS表征表明，电极表面由Co₃O₄和Cu²⁺组成；SEM和EDS表征发现质量分数约7.85%的Cu元素负载在了Co₃O₄纳米条上；利用线性扫描伏安法测试了电极对于水中NO₃ ^--N的电催化还原能力，发现其电流响应密度较大，表现出了较强的电化学活性。将其用于电催化还原去除水中硝酸盐，结果表明，在pH=7、电流密度10 mA/cm²、NO₃ ^--N初始质量浓度50 mg/L条件下电解2 h后NO₃ ^--N去除率达到99.73%；电极可以在较大酸碱范围内工作，中性和酸性条件下比在碱性条件下电化学还原效果更好；此外，当添加质量浓度为1 000 mg/L的Cl^-时，可以获得93.7%的总氮去除率。添加叔丁醇（TBA）的原子氢清除实验表明，该电极催化体系对NO₃ ^--N的还原基本沿直接电子还原路径进行。稳定性评价实验表明，CuO-Co₃O₄@TBNE电极在10次循环实验中表现出了较好的稳定性以及极低的金属浸出量。

关键词: 四氧化三钴, 钛基纳米电极, 硝酸盐, 电催化, 金属有机框架

CLC Number:

X703

Songlin LIU, Qingfeng YANG, Huiqiang QIU, Yuwen SUN, Yangqiao LIU. Investigation of nitrate removal in water by CuO-Co₃O₄ modified titanium-based nanoelectrode[J]. Industrial Water Treatment, 2025, 45(2): 46-53.

刘松麟, 杨庆峰, 邱辉强, 孙宇雯, 刘阳桥. CuO-Co₃O₄改性钛基纳米电极去除水中硝酸盐[J]. 工业水处理, 2025, 45(2): 46-53.

/ / Recommend / Download Citations

URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2024-0068

https://www.iwt.cn/EN/Y2025/V45/I2/46

Figures/Tables 8

Fig.1 XRD patterns

Fig.2 XPS of CuO-Co₃O₄@TBNE in the Cu 2p range

Fig.3 SEM of TBNE，and SEM-EDS of CuO-Co₃O₄@TBNE

Fig.4 LSV curves of different electrode materials

Fig.5 NO₃ ^- reduction performances of different electrode materials

Fig.6 Effects of current density （a），initial NO₃ ^--N concentration （b）， initial pH （c），and Cl^- concentration （d） on the electrochemical reduction of NO₃ ^--N

Fig.7 The removal efficiencies of NO₃ ^--N by the system under different TBA concentrations

Fig.8 Cyclic experiment

References 31

1	YU Chaoqing， HUANG Xiao， CHEN Han，et al. Managing nitrogen to restore water quality in China［J］. Nature，2019，567（7749）：516-520. doi:10.1038/s41586-019-1001-1
2	中华人民共和国生态环境部，国家统计局，中华人民共和国农业农村部. 第二次全国污染源普查公报［R/OL］. 2020-06-08. doi:10.1055/s-0040-1721631
3	WANG Xiaowei， TAN Xin， DANG Chengcheng，et al. Thermophilic microorganisms involved in the nitrogen cycle in thermal environments：Advances and prospects［J］. Science of the Total Environment，2023，896：165259. doi:10.1016/j.scitotenv.2023.165259
4	WANG Jiahong， SHARAF F， KANWAL A. Nitrate pollution and its solutions with special emphasis on electrochemical reduction removal［J］. Environmental Science and Pollution Research International，2023，30（4）：9290-9310. doi:10.1007/s11356-022-24450-2
5	LIU Yong， ZHANG Xuemei， WANG Jianlong. A critical review of various adsorbents for selective removal of nitrate from water：Structure，performance and mechanism［J］. Chemosphere，2022，291（Pt 1）：132728. doi:10.1016/j.chemosphere.2021.132728
6	SCHOLES R C， VEGA M A， SHARP J O，et al. Nitrate removal from reverse osmosis concentrate in pilot-scale open-water unit process wetlands［J］. Environmental Science：Water Research & Technology，2021，7（3）：650-661. doi:10.1039/d0ew00911c
7	ZHANG Zhengwen， XU Chunyan， HAN Hongjun，et al. Effect of low-intensity electric current field and iron anode on biological nitrate removal in wastewater with low COD to nitrogen ratio from coal pyrolysis［J］. Bioresource Technology，2020，306：123123. doi:10.1016/j.biortech.2020.123123
8	CURCIO G M， LIMONTI C， SICILIANO A，et al. Nitrate removal by zero-valent metals：A comprehensive review［J］. Sustainability，2022，14（8）：4500. doi:10.3390/su14084500
9	WANG Yuting， WANG Changhong， LI Mengyang，et al. Nitrate electroreduction：Mechanism insight，in situ characterization，performance evaluation，and challenges［J］. Chemical Society Reviews，2021，50（12）：6720-6733. doi:10.1039/d1cs00116g
10	ZENG Yachao， PRIEST C， WANG Guofeng，et al. Restoring the nitrogen cycle by electrochemical reduction of nitrate：Progress and prospects［J］. Small Methods，2020，4（12）：2000672. doi:10.1002/smtd.202000672
11	WANG Zixuan， RICHARDS D， SINGH N. Recent discoveries in the reaction mechanism of heterogeneous electrocatalytic nitrate reduction［J］. Catalysis Science & Technology，2021，11（3）：705-725. doi:10.1039/d0cy02025g
12	HE Anbang， YANG Yong， TAO Shuhui，et al. In situ encapsulated Co₃O₄ nanoparticles into self-catalyzed grown CNTs for efficient CO₂ conversion［J］. Fuel，2024，358：130057. doi:10.1016/j.fuel.2023.130057
13	BAI Yarong， DONG Junping， HOU Yaqin，et al. Co₃O₄@PC derived from ZIF-67 as an efficient catalyst for the selective catalytic reduction of NO _x with NH₃ at low temperature［J］. Chemical Engineering Journal，2019，361：703-712. doi:10.1016/j.cej.2018.12.109
14	聂华芳，杨庆峰，刘登科，等. Co₃O₄-钛基纳米电极去除工业废水中硝酸盐的研究［J］. 工业水处理，2022，42（10）：84-90.
	NIE Huafang， YANG Qingfeng， LIU Dengke，et al. Co₃O₄-titanium-based nanoelectrode for nitrate removal from industrial wastewater［J］. Industrial Water Treatment，2022，42（10）：84-90.
15	GAO Jianan， JIANG Bo， NI Congcong，et al. Enhanced reduction of nitrate by noble metal-free electrocatalysis on P doped three-dimensional Co₃O₄ cathode：Mechanism exploration from both experimental and DFT studies［J］. Chemical Engineering Journal，2020，382：123034. doi:10.1016/j.cej.2019.123034
16	LIU Jinxun， RICHARDS D， SINGH N，et al. Activity and selectivity trends in electrocatalytic nitrate reduction on transition metals［J］. ACS Catalysis，2019，9（8）：7052-7064. doi:10.1021/acscatal.9b02179
17	WU Shaorui， LIU Jingbing， WANG Hao，et al. A review of performance optimization of MOF-derived metal oxide as electrode materials for supercapacitors［J］. International Journal of Energy Research，2019，43（2）：697-716. doi:10.1002/er.4232
18	SONG Qinan， ZHANG Shuo， HOU Xiaoshu，et al. Efficient electrocatalytic nitrate reduction via boosting oxygen vacancies of TiO₂ nanotube array by highly dispersed trace Cu doping［J］. Journal of Hazardous Materials，2022，438：129455. doi:10.1016/j.jhazmat.2022.129455
19	李翔飞. CuO及其复合物活化PMS降解有机污染物性能及机理研究［D］. 恩施：湖北民族大学，2024. doi:10.1016/j.jclepro.2023.136468
	LI Xiangfei. Study on the performance and mechanism of CuO and its complex activated PMS degradation of organic pollutants［D］. Enshi：Hubei Minzu University，2024. doi:10.1016/j.jclepro.2023.136468
20	KUMAR P， INWATI G K， MATHPAL M C，et al. Defects induced enhancement of antifungal activities of Zn doped CuO nanostructures［J］. Applied Surface Science，2021，560：150026. doi:10.1016/j.apsusc.2021.150026
21	AWUAL M R， ASIRI A M， RAHMAN M M，et al. Assessment of enhanced nitrite removal and monitoring using ligand modified stable conjugate materials［J］. Chemical Engineering Journal，2019，363：64-72. doi:10.1016/j.cej.2019.01.125
22	GAO Jianan， JIANG Bo， NI Congcong，et al. Non-precious Co₃O₄-TiO₂/Ti cathode based electrocatalytic nitrate reduction：Preparation，performance and mechanism［J］. Applied Catalysis B：Environmental，2019，254：391-402. doi:10.1016/j.apcatb.2019.05.016
23	LIMA A S， SALLES M O， FERREIRA T L，et al. Scanning electrochemical microscopy investigation of nitrate reduction at activated copper cathodes in acidic medium［J］. Electrochimica Acta，2012，78：446-451. doi:10.1016/j.electacta.2012.06.075
24	GARCIA-SEGURA S， LANZARINI-LOPES M， HRISTOVSKI K，et al. Electrocatalytic reduction of nitrate：Fundamentals to full-scale water treatment applications［J］. Applied Catalysis B：Environmental，2018，236：546-568. doi:10.1016/j.apcatb.2018.05.041
25	WANG Jing， FENG Tao， CHEN Jiaxin，et al. Electrocatalytic nitrate/nitrite reduction to ammonia synthesis using metal nanocatalysts and bio-inspired metalloenzymes［J］. Nano Energy，2021，86：106088. doi:10.1016/j.nanoen.2021.106088
26	LIU Xinrui， GUO Rui， QIN Xia，et al. Enhanced selective nitrate-to-nitrogen electrocatalytic reduction by CNTs doped Ni foam/Cu electrode coupled with Cl^- ［J］. Journal of Water Process Engineering，2023，54：104067. doi:10.1016/j.jwpe.2023.104067
27	WU Tianyi， KONG Xiangang， TONG Siyuan，et al. Self-supported Cu nanosheets derived from CuCl-CuO for highly efficient electrochemical degradation of NO₃ ^- ［J］. Applied Surface Science，2019，489：321-329. doi:10.1016/j.apsusc.2019.05.358
28	MAO Ran， LI Ning， LAN Huachun，et al. Dechlorination of trichloroacetic acid using a noble metal-free graphene-Cu foam electrode via direct cathodic reduction and atomic H［J］. Environmental Science & Technology，2016，50（7）：3829-3837. doi:10.1021/acs.est.5b05006
29	WANG Jiahong， ZHANG Zhen， WANG Si. Facile fabrication of Ag/GO/Ti electrode by one-step electrodeposition for the enhanced cathodic reduction of nitrate pollution［J］. Journal of Water Process Engineering，2021，40：101839. doi:10.1016/j.jwpe.2020.101839
30	KUANG Peijing， FENG Chuanping， LI Miao，et al. Improvement on electrochemical reduction of nitrate in synthetic groundwater by reducing anode surface area［J］. Journal of the Electrochemical Society，2017，164（6）：E103-E112. doi:10.1149/2.0831706jes
31	WU Yudong， LU Kunkun， XU Lianhua. Progress and prospects of electrochemical reduction of nitrate to restore the nitrogen cycle［J］. Journal of Materials Chemistry A，2023，11（33）：17392-17417. doi:10.1039/d3ta01592k

[1]	Wei HOU, Xiao ZHANG, Bowei ZHAO. A feasibility study of simultaneous sewage treatment and hydrogen production by electrolyzing water using NiCo₂O₄/NF anode [J]. Industrial Water Treatment, 2025, 45(2): 71-77.
[2]	Xianchun PENG, Lili ZHENG, Haoran LU, Zhefeng WANG, Zheng ZHU, Wenyan LIANG. Performance of sulfur/steel slag composite matrix in removing nitrate from surface water with low-carbon content [J]. Industrial Water Treatment, 2025, 45(1): 41-48.
[3]	Juan LI, Min LIU, Ying CHEN, Junchao TIAN. Construction and simulation comparison of sectional combined evaporation system for sodium nitrate wastewater [J]. Industrial Water Treatment, 2024, 44(9): 169-175.
[4]	Changyi LIU, Jiawang TIAN, Haodong ZHANG, Zhe QIN. Investigation on the adsorption and denitrification performance of modified reed material and its resource utilization [J]. Industrial Water Treatment, 2024, 44(8): 122-132.
[5]	Jinfeng FANG, Ying QU, Yubo ZHAO, Rupeng LIU, Zhen ZHANG, Zhen QI, Haoyu FAN, Weichen ZHU. Research progress of nitrate removal from water via capacitive deionization [J]. Industrial Water Treatment, 2024, 44(7): 29-37.
[6]	Huixia ZHANG, Chenxin XIE, Lishan ZHOU, Chunyan REN, Hui ZHAO, Taiping LEI, Lingzhi ZHU. Preparation and photo-electrocatalytic performance of Ag-Ti³⁺-TiO₂ nanocone [J]. Industrial Water Treatment, 2024, 44(3): 159-167.
[7]	Huchun XU, Hui YANG, Ting YU, Junbo ZHANG, Zhongtai CHEN, Siya WANG, Yuxin SUN, Guangjing XU. Research progress on solid slow-release carbon source for enhancing wastewater nitrogen removal [J]. Industrial Water Treatment, 2024, 44(12): 20-30.
[8]	Weiqiu YANG, Guangyu SHI. A project case on treatment of photovoltaic enterprise production wastewater [J]. Industrial Water Treatment, 2024, 44(11): 172-176.
[9]	Hua YAN, Changzi GUO, Wanqin ZHAO, Xuli ZHANG, Yi HAN, Yixu WANG. Simultaneous nitrogen and sulphur removal effect and functional bacteria of sulfur-driven autotrophic denitrification ASBR process [J]. Industrial Water Treatment, 2024, 44(10): 151-157.
[10]	Jiawang TIAN, Shanshan HE, Tao ZHANG, Zhe QIN. Preparation and nitrogen removal performance of magnetic amine-crosslinked biopolymer based reed straw [J]. Industrial Water Treatment, 2024, 44(1): 138-147.
[11]	Hui ZHAO, Fudong WANG, Guanglei QIAN, Taiping LEI, Chunyan REN, Chenxin XIE. Research progress of electrocatalytic reduction of nitrate in wastewater to ammonia [J]. Industrial Water Treatment, 2024, 44(1): 60-72.
[12]	Yafeng LI, Siding XU, Chong GAO, Xiangyu FU. Treatment of reactive brilliant orange X-GN wastewater by three-dimensional electrode-electro-Fenton method [J]. Industrial Water Treatment, 2024, 44(1): 80-87.
[13]	Qingkong CHEN, Yifei LEI, Zhijun CHEN, Huan WANG, Jianping FAN, Shanze LI, Dianchang WANG. Degradation of methyl orange in water by persulfate catalyzed with carbonized ZIF-67 [J]. Industrial Water Treatment, 2023, 43(8): 89-96.
[14]	Xiao WANG, Weichao MA, Lei ZHAO, Zhilun LIU, Jun MA, Peng CHANG. Study on catalytic ozonation by Co₃O₄ for the degradation of ketoprofen in aqueous solution [J]. Industrial Water Treatment, 2023, 43(7): 94-103.
[15]	Dandan XU. Discussion on the determination of nitrate nitrogen by total nitrogen channel in flow injection analyzer [J]. Industrial Water Treatment, 2023, 43(5): 158-161.

Please choose a citation manager

Content to export

Investigation of nitrate removal in water by CuO-Co₃O₄ modified titanium-based nanoelectrode

CuO-Co₃O₄改性钛基纳米电极去除水中硝酸盐

RichHTML

PDF

Knowledge

Cited

Abstract

Cite this article

share this article

Figures/Tables 8

References 31

Related Articles 15

Recommended Articles

Metrics

Comments

模态框（Modal）标题

Please choose a citation manager

Content to export