Efficient electrochemical bromate reduction using cobalt phosphide self-supported cobalt foam electrode

SHEN Jian; YAO Fubing; CHEN Shengjie; YANG Qi

doi:10.12030/j.cjee.202111061

2022 Volume 16 Issue 3

Article Contents

Previous Article Next Article

SHEN Jian, YAO Fubing, CHEN Shengjie, YANG Qi. Efficient electrochemical bromate reduction using cobalt phosphide self-supported cobalt foam electrode[J]. Chinese Journal of Environmental Engineering, 2022, 16(3): 894-905. doi: 10.12030/j.cjee.202111061

Citation:

SHEN Jian, YAO Fubing, CHEN Shengjie, YANG Qi. Efficient electrochemical bromate reduction using cobalt phosphide self-supported cobalt foam electrode[J]. Chinese Journal of Environmental Engineering, 2022, 16(3): 894-905. doi: 10.12030/j.cjee.202111061

Efficient electrochemical bromate reduction using cobalt phosphide self-supported cobalt foam electrode

1.
He' nan Province Aorui Environmental Protection Technology Co. Ltd., Zhengzhou 450000, China
2.
College of Environmental Science and Engineering, Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082, China
3.
School of Metallurgy and Environment, Central South University, National Engineering Research Center for Heavy Metal Pollution Control, Changsha 410083, China

Corresponding author: YANG Qi, yangqi@hnu.edu.cn
Received Date: 11/11/2021
Available Online: 10/03/2022

Abstract

Exploring highly active and inexpensive electrode are the keys in electrochemical reduction of bromate (${\rm{BrO}}_3^ - $). Although the noble metal-based electrode has attracted intensive attention for its high activity, low abundance and high price of noble metal seriously impede its practical application. In this study, a binder-free composite electrode (CoP/CF) was prepared by direct growth of cobalt phosphide(CoP) on cobalt foam(CF) and then was used to perform electrochemical reduction of ${\rm{BrO}}_3^ - $. The results showed that CoP/CF-350 electrode prepared at 350 ℃ had a better electrochemical performance on high ${\rm{BrO}}_3^ - $ reduction(97.6%) and lower energy consumption (0.014 kWh·mg⁻¹) at the initial ${\rm{BrO}}_3^ - $ concentration of 250 μg·L⁻¹ and current density of 5.0 mA·cm⁻². The cyclic voltammetry(CV) and quenching experiments demonstrated that ${\rm{BrO}}_3^ - $ removal should be ascribed to the synergistic effect of direct electron transfer and active hydrogen (H^*) indirect reduction. The in-situ grown CoP served as the bifunctional catalyst and played the dual roles of electron mediator and bridge, further enhanced the ${\rm{BrO}}_3^ - $ reduction. Even after five cyclic experiments, the CoP/CF-350 electrode still remained a good electrocatalytic activity, this indicated that this electrode had a good stability.
- CoP,
- self-supported electrode,
- electrochemical reduction,
- ${\rm{BrO}}_3^ - $,
- reaction mechanism

References

[1]	武琳, 杨宏伟, 杨少霞, 等. 催化臭氧氧化过程中溴酸盐的生成机制研究[J]. 环境科学, 2011, 32(8): 2281-2283. Google Scholar Pub Med
[2]	LI Y K, SHEN W H, FU S J, et al. Inhibition of bromate formation during drinking water treatment by adapting ozonation to electro- peroxone process[J]. Chemical Engineering Journal, 2017, 264: 322-328. Google Scholar Pub Med
[3]	王执伟, 刘冬梅, 张文娟, 等. 溴酸盐对水生生物的急性毒性效应[J]. 环境科学, 2016, 37(2): 756-764. Google Scholar Pub Med
[4]	钟宇, 杨麒, 李小明, 等. RBER生物降解溴酸盐及微生物群落结构分析[J]. 中国环境科学, 2017, 37(5): 1945-1953. doi: 10.3969/j.issn.1000-6923.2017.05.043 CrossRef Google Scholar Pub Med
[5]	ZHONG Y, LI X M, YANG Q, et al. Complete bromate and nitrate reduction using hydrogen as the sole electron donor in a rotating biofilm-electrode reactor[J]. Journal of Hazardous Materials, 2016, 307: 82-90. doi: 10.1016/j.jhazmat.2015.12.053 CrossRef Google Scholar Pub Med
[6]	WU X Q, YANG Q, XU D C, et al. Simultaneous adsorption/reduction of bromate by nanoscale zerovalent iron supported on modified activated carbon[J]. Industrial & Engineering Chemistry Research, 2013, 52: 12574-12581. Google Scholar Pub Med
[7]	YURANOVA T, KIWI-MINSKER L, FRANCH C, et al. Nanostructured catalysts for the continuous reduction of nitrates and bromates in Water[J]. Industrial & Engineering Chemistry Research, 2013, 52: 13930-13937. Google Scholar Pub Med
[8]	CHEN F, YANG Q, ZHONG Y, et al. Photo-reduction of bromate in drinking water by metallic Ag and reduced graphene oxide (RGO) jointly modified BiVO₄ under visible light irradiation[J]. Water Research, 2016, 101: 555-563. doi: 10.1016/j.watres.2016.06.006 CrossRef Google Scholar Pub Med
[9]	安东, 宋佳秀, 乐林生, 等. 溴离子和溴酸盐活性炭竞争吸附及溴酸盐生成影响[J]. 环境科学, 2008, 29(4): 948-953. doi: 10.3321/j.issn:0250-3301.2008.04.018 CrossRef Google Scholar Pub Med
[10]	李昂臻, 冒冉, 赵旭. 泡沫铜电极电还原去除溴酸盐研究[J]. 中国科学, 2014, 44(10): 1675-1681. Google Scholar Pub Med
[11]	MAO R, ZHAO X, QU J H, et al. Electrochemical reduction of bromate by a Pd modified carbon fiber electrode: Kinetics and mechanism[J]. Electrochemical Acta, 2014, 132: 151-157. doi: 10.1016/j.electacta.2014.03.170 CrossRef Google Scholar Pub Med
[12]	MAO R, ZHAO X, LAN H C, et al. Graphene-modified Pd/C cathode and Pd/GAC particles for enhanced electrocatalytic removal of bromate in a continuous three-dimensional electrochemical reactor[J]. Water Research, 2015, 77: 1-12. doi: 10.1016/j.watres.2015.03.002 CrossRef Google Scholar Pub Med
[13]	LAN H C, MAO R, TONG Y T, et al. Enhanced electroreductive removal of bromate by a supported Pd-In bimetallic catalyst: Kinetics and mechanism investigation[J]. Environmental Science & Technology, 2016, 50: 11872-11878. Google Scholar Pub Med
[14]	SHEN W J, LIN F J, JIANG X, et al. Efficient removal of bromate with core-shell Fe@Fe₂O₃ nanowires[J]. Chemical Engineering Journal, 2017, 308: 880-888. doi: 10.1016/j.cej.2016.09.070 CrossRef Google Scholar Pub Med
[15]	YUAN C Z, ZHONG S L, JIANG Y F, et al. Direct growth of cobalt-rich cobalt phosphide catalysts on cobalt foil: an efficient and self-supported bifunctional electrode for overall water splitting in alkaline media[J]. Journal of Materials Chemistry A, 2017, 5: 10561-10566. doi: 10.1039/C7TA01776F CrossRef Google Scholar Pub Med
[16]	LIU H L, HAN J L, YUAN J L, et al. Deep dehalogenation of florfenicol using crystalline CoP nanosheet arrays on a Ti plate via direct cathodic reduction and atomic H[J]. Environmental Science & Technology, 2019, 53: 11932-11940. Google Scholar Pub Med
[17]	MISUDOME T, SHENG M, NAKATA A, et al. A cobalt phosphide catalyst for the hydrogenation of nitriles[J]. Chemical Science, 2020, 11: 6682-6689. doi: 10.1039/D0SC00247J CrossRef Google Scholar Pub Med
[18]	LIU D N, CHEN T, ZHU W X, et al. Cobalt phosphide nanowires: An efficient electrocatalyst for enzymeless hydrogen peroxide detection[J]. Nanotechnology, 2016, 27: 33LT01. doi: 10.1088/0957-4484/27/33/33LT01 CrossRef Google Scholar Pub Med
[19]	LIU Z W, DONG S S, ZOU D, et al. Electrochemically mediated nitrate reduction on nanoconfined zerovalent iron: Properties and mechanism[J]. Water Research, 2020, 173: 115595. Google Scholar Pub Med
[20]	SU L, HAN D D, ZHU G J, et al. Tailoring the assembly of iron nanoparticles in carbon microspheres toward high-performance electrocatalytic denitrification[J]. Nano Letters, 2019, 19: 5423-5430. doi: 10.1021/acs.nanolett.9b01925 CrossRef Google Scholar Pub Med
[21]	CHEN X T, ZHANG T, KAN M, et al. Binderless and oxygen vacancies rich FeNi/graphitized mesoporous carbon/Ni foam for electrocatalytic reduction of nitrate[J]. Environmental Science & Technology, 2020, 54: 13344-13353. Google Scholar Pub Med
[22]	YAO Q F, ZHOU X F, XIAO S Z, et al. Amorphous nickel phosphide as a noble metal-free cathode for electrochemical dechlorination[J]. Water Research, 2019, 165: 114930. doi: 10.1016/j.watres.2019.114930 CrossRef Google Scholar Pub Med
[23]	YAO F B, YANG Q, YAN M, et al. Synergistic adsorption and electrocatalytic reduction of bromate by Pd/N-doped loofah sponge-derived biochar electrode[J]. Journal of Hazardous Materials, 2020, 386: 121651. doi: 10.1016/j.jhazmat.2019.121651 CrossRef Google Scholar Pub Med
[24]	ZHANG X, WANG Y T, LIU C B, et al. Recent advances in non-noble metal electrocatalysts for nitrate reduction[J]. Chemical Engineering Journal, 2021, 403: 126269. doi: 10.1016/j.cej.2020.126269 CrossRef Google Scholar Pub Med
[25]	PFEIFFER H, TANCRET F, BICHAT M P, et al. Air stable copper phosphide (Cu₃P): A possible negative electrode material for lithium batteries[J]. Electrochemistry Communications, 2004, 6: 263-267. doi: 10.1016/j.elecom.2003.12.012 CrossRef Google Scholar Pub Med
[26]	ZHUANG M H, OU X W, DOU Y B, et al. Polymer-embedded fabrication of Co₂P nanoparticles encapsulated in N, P-doped graphene for hydrogen generation[J]. Nano Letters, 2016, 16: 4691-4698. doi: 10.1021/acs.nanolett.6b02203 CrossRef Google Scholar Pub Med
[27]	JIANG N, YOU B, SHENG M L, et al. Electrodeposited cobalt-phosphorous-derived films as competent bifunctional catalysts for overall water splitting[J]. Angewandte Chemie-International Edition, 2015, 54: 6251-6254. doi: 10.1002/anie.201501616 CrossRef Google Scholar Pub Med
[28]	SHIH Y J, WU Z L, HUANG Y H, et al. Electrochemical nitrate reduction as affected by the crystal morphology and facet of copper nanoparticles supported on nickel foam electrodes (Cu/Ni)[J]. Chemical Engineering Journal, 2020, 383: 123157. doi: 10.1016/j.cej.2019.123157 CrossRef Google Scholar Pub Med
[29]	YAO F B, JIA M C, YANG Q, et al. Highly selective electrochemical nitrate reduction using copper phosphide self-supported copper foam electrode: Performance, mechanism, and application[J]. Water Research, 2021, 193: 116881. doi: 10.1016/j.watres.2021.116881 CrossRef Google Scholar Pub Med
[30]	KISHIMOTO N, MATSUDA N. Bromate ion removal by electrochemical reduction using an activated carbon felt electrode[J]. Environmental Science & Technology, 2009, 43: 2054-2059. Google Scholar Pub Med
[31]	MAO R, ZHAO X, LAN H C, et al. Efficient electrochemical reduction of bromate by a Pd/rGO/CFP electrode with low applied potentials[J]. Applied Catalysis B:Environmental, 2014, 160: 179-187. Google Scholar Pub Med
[32]	GAO J N, JIANG B, NI C C, 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 CrossRef Google Scholar Pub Med
[33]	GAO J N, JIANG B, NI C C, et al. Co₃O₄-TiO₂/Ti cathode based electrocatalytic nitrate reduction: Preparation, performance and mechanism[J]. Applied Catalysis B: Environmental, 2019, 254: 391-402. Google Scholar Pub Med
[34]	LIU C, ZHANG A Y, PEI D N, et al. Efficient electrochemical reduction of nitrobenzene by defect engineered TiO_2-x single crystals[J]. Environmental Science & Technology, 2016, 50: 5234-5242. Google Scholar Pub Med
[35]	LI Y H, LIU P F, PAN L F, et al. Local atomic structure modulations activate metal oxide as electrocatalyst for hydrogen evolution in acidic water[J]. Nature Communications, 2015, 6: 8064 Google Scholar Pub Med
[36]	YAO F B, YANG Q, JIAN S, et al. Electrochemical reduction of bromate using noble metal-free nanoscale zero-valent iron immobilized activated carbon fiber electrode[J]. Chemical Engineering Journal, 2020, 389: 123588 Google Scholar Pub Med

Access History

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Figures(9) / Tables(1)

Export Citation

PDF

XML

Article Metrics

Article views(3938) PDF downloads(88) Cited by(0)

Access History

HTML

溴酸盐(${\rm{BrO}}_3^ - $)是含溴离子(Br⁻)水体在臭氧或氯气消毒过程中生成的一种消毒副产物^[1]。在经臭氧消毒的饮用水中检测到BrO₃⁻的质量浓度可达到120 μg·L^−1[2]。${\rm{BrO}}_3^ - $具有较强的DNA损伤能力，可引起肾肿瘤和腹膜间皮瘤等疾病^[3]。因此，世界卫生组织(WHO)规定饮用水中${\rm{BrO}}_3^ - $质量浓度应低于10 μg·L⁻¹。目前，很多技术被应用于水体中${\rm{BrO}}_3^ - $的去除，包括生物修复^[4-5]、化学/催化还原^[6-7]、光催化还原^[8]、物理分离^[9]等。然而这些技术存在二次污染、运行和维护成本高以及操作复杂等缺点。近年来，电化学还原技术因其反应速度快、无污染、操作便捷等优点，在控制水体中BrO₃⁻污染方面已有较多应用^[10]。

在电化学还原${\rm{BrO}}_3^ - $体系中，阴极材料处于“心脏”地位，是实现高效率和低能耗去除BrO₃⁻的关键。常用的电极材料有贵金属基(Pd、Ir、Pt等)^[11-13]和非贵金属基(Fe、Cu等)^[6,14]两大类。MAO等采用氧化还原石墨烯修饰碳纸负载钯纳米颗粒阴极(Pd-rGO/C)，并耦合活性炭负载钯(Pd/GAC)颗粒电极，在恒定电流条件下可将${\rm{BrO}}_3^ - $还原成为Br⁻离子^[12]。然而贵金属价格昂贵，目前对其研究仅仅停留在实验室阶段。因此，开发具有高活性且廉价的非贵金属基电极材料已受到更广泛的关注。

${\rm{BrO}}_3^ - $的电化学还原包括2种作用，即电子的直接还原和活性氢(H^*)介导的间接还原^[13]。泡沫钴(cobalt foam, CF)由于成本低廉、比表面积大、稳定性高等优点，被认为是优良的电极材料^[15]。但CF电子传递速率差和催化产生H^*的活性较低，导致其电化学还原${\rm{BrO}}_3^ - $的性能较差。因此，能否在保留CF自身优点的基础上提升其催化产生H^*的性能和电子传递速率是一个值得研究的课题。磷化钴(CoP)具有独特的电子结构，不仅可以作为电子媒介促进电子传递，还能作为催化剂电催化产生H^*[16-18]。LIU等在以CoP作为阴极开展氟苯尼考电化学脱卤的研究中发现CoP确实能促进电子传递和H^*的形成^[16]。受上述结果启发，将CoP与CF结合有望得到一种活性高和稳定性佳的复合电极。通常，研究者会利用聚偏氟乙二烯、聚四氟乙烯等高分子化合物粘结剂将催化剂负载于电极表面，但粘结剂的使用会严重影响活性物质的催化性能和电极的稳定性^[19-20]。为此，无粘结剂的催化剂和电极耦合技术是制备复合电极的热门方法^[21-23]。

本研究以CF作为基底，通过原位生长制备CoP与CF耦合自支撑电极(CoP/CF)，该电极不使用粘结剂，增加了电子传递速率和电催化产H*性能，具备较好的电还原${\rm{BrO}}_3^ - $性能。本研究通过优化电极制备条件，调控其还原${\rm{BrO}}_3^ - $性能，并探讨其机制，以期为电催化还原${\rm{BrO}}_3^ - $提供参考。

3. 结论

1)当磷化温度为350 ℃时，CoP/CF自支撑电极对$ {\rm{BrO}}_3^ - $展现出最佳的还原性能，对初始质量浓度为250 μg·L⁻¹的$ {\rm{BrO}}_3^ - $，去除率最高可达97.6%。

2) CoP/CF自支撑电极电化学还原$ {\rm{BrO}}_3^ - $时，$ {\rm{BrO}}_3^ - $初始浓度越高，去除的绝对量越大，同时还原1 mg $ {\rm{BrO}}_3^ - $需要的电能越低；电流密度越大，$ {\rm{BrO}}_3^ - $去除率越高，但相应的能耗也越高；DO对CoP/CF自支撑电极影响不大。

3) CoP/CF自支撑电极电化学还原$ {\rm{BrO}}_3^ - $的产物为Br⁻，并没有其他副产物的积累；在以CoP/CF为阴极构建的电化学系统中，$ {\rm{BrO}}_3^ - $的去除包括直接电子还原和H^*介导的间接还原；CV分析表明$ {\rm{BrO}}_3^ - $的还原是一个受扩散传质控制的过程；在还原过程中CoP不仅作为电子传递媒介或桥梁促进电子传递，还可以作为电催化剂催化产生H^*并用于$ {\rm{BrO}}_3^ - $的加氢还原。

4) CoP/CF自支撑电极在循环5次后仍然保持较高的电化学活性。

Figure (9) Table (1) Reference (36)

Efficient electrochemical bromate reduction using cobalt phosphide self-supported cobalt foam electrode

Abstract

References

Access History

通讯作者: 陈斌, bchen63@163.com

Article Metrics

Access History