构筑锆基活性位点用于电吸附磷酸盐的研究

doi:10.19965/j.cnki.iwt.2023-0239

摘要/Abstract

摘要：

水体中含有过量的磷会导致富营养化等环境污染问题，有效去除磷酸盐的方法引发了研究者们的关注。通过液相浸渍耦合焙烧法成功制备了Zr基金属掺杂的活性炭电极材料（ZrAC），并将其用于电吸附除磷。通过XRD、XPS、SEM、EDS及TEM表征了该复合活性炭材料，结果表明，所合成的ZrAC材料具有良好的晶体结构特征，Zr的负载为磷酸盐去除提供了充足的吸附位点。所制备的电极材料对磷酸盐的去除符合伪二级动力学模型，在1.0 V的电压下，电极对PO₄ ^3-的吸附量可达到29.43 mg/g，外接电压显著提升了对磷酸盐的去除性能，ZrO₂对PO₄ ^3-的捕获主要源于Zr—O—P键的形成，由此提升了电极材料对PO₄ ^3-的吸附能力和速度。此外，所合成的ZrAC电极材料在电吸附过程中具有较好的抗干扰能力和稳定性。

关键词: 电吸附, 磷酸盐去除, 富营养化, 氧化锆

Abstract:

Excessive phosphorus in water can lead to environmental pollution problems such as eutrophication，and effective methods for removing phosphate have attracted the attention of researchers. The electrode material（ZrAC） of Zr-based metal doped activated carbon was successfully prepared by liquid-phase impregnation coupled calcination method and used for phosphorus electro-adsorption. The composite activated carbon material was characterized by XRD，XPS，SEM，EDS and TEM. The results indicated that the synthesized ZrAC material exhibited favorable crystal structure characteristics，while the incorporation of Zr provided an ample number of adsorption sites for efficient phosphate removal. The kinetics of the prepared electrode material during the phosphate removal process followed a pseudo-second-order kinetic model. At a voltage of 1.0 V，the PO₄ ^3- electro-adsorption capacity could reach 29.43 mg/g，and the external voltage significantly improved the phosphate removal effect. The capture of PO₄ ^3- by ZrAC was primarily attributed to the formation of Zr—O—P bond，thereby enhancing the adsorption capacity and rate of the electrode material towards PO₄ ^3-. Moreover，the synthesized ZrAC electrode material exhibited excellent resistance to interference and stability during electro-adsorption.

Key words: electro-adsorption, phosphate removal, eutrophication, zirconia

中图分类号:

TQ424
X703.1

伏培仟, 张鹏, 卜兆宇, 李克勋. 构筑锆基活性位点用于电吸附磷酸盐的研究[J]. 工业水处理, 2024, 44(3): 74-80.

Peiqian FU, Peng ZHANG, Zhaoyu BU, Kexun LI. Construction of zirconium-based active site for phosphate electro-adsorption[J]. Industrial Water Treatment, 2024, 44(3): 74-80.

https://www.iwt.cn/CN/Y2024/V44/I3/74

图/表 10

图1 电极材料的XRD

Fig.1 XRD of the electrode materials

图2 电极材料的拉曼光谱

Fig.2 Raman spectra of the electrode materials

图3 电极材料的XPS

Fig.3 XPS of electrode materials

图4 电极材料的形貌分析（a） AC材料的SEM；（b） ZrAC材料的SEM；（c）~（e） ZrAC材料的EDS mapping元素图谱；（f）~（h） ZrAC材料的TEM。

Fig.4 Morphological analysis of electrode materials

图5 电极材料用于PO₄ ^3-电吸附的效果以及动力学拟合

Fig.5 Effectiveness of the electrodes for electro-adsorption of PO₄ ^3- and kinetic fit

表1 电极材料电吸附PO₄ ^3-的动力学拟合参数

Table 1 Kinetic fitting parameters of PO₄ ^3- electro-adsorption by electrode materials

电极材料

伪一级动力学

伪二级动力学

q _e/

（mg·g^-1）

k ₁/

min^-1

R ²

q _e/

（mg·g^-1）

k ₂/

（g·mg^-1·min^-1）

表2 已报道的磷酸盐去除材料

Table 2 Reported materials for phosphate removal

吸附剂/电极	吸附量/（mg·g^-1）	时间/h	文献
Ca/Fe-3/1	4.83（以P计）	2	〔19〕
Mg₂Al₁-Cl	21.05（以PO₄ ^3-计）	2	〔20〕
ZrO₂@Fe₃O₄	~4（以P计）	3	〔21〕
PANI/TiO₂	4.99（以P计）	1	〔22〕
Mg-Cr LDHs/AC	41.09（以PO₄ ^3-计）	8	〔23〕
UiO-66（Hydrochloric acid）	22.13（以PO₄ ^3-计）	1	〔24〕
ZrAC	29.43（以PO₄ ^3-计）	0.5	本研究

图6 不同电压下ZrAC电极材料用于PO₄ ^3-电吸附的效果

Fig.6 PO₄ ^3- electro-adsorption effect by ZrAC electrodewith different voltages

图7 不同阴离子存在下ZrAC电极材料对PO₄ ^3-的电吸附效果

Fig.7 PO₄ ^3- electro-adsorption effect by ZrAC electrodewith different co-existent anions

图8 ZrAC电极材料的循环使用性能

Fig.8 Recycling performance of ZrAC electrode material

参考文献 27

1	WU Baile， WAN Jun， ZHANG Yanyang，et al. Selective phosphate removal from water and wastewater using sorption：Process fundamentals and removal mechanisms［J］. Environmental Science & Technology，2020，54（1）：50-66. doi:10.1021/acs.est.9b05569
2	LIU Da， GU Wenyi， ZHOU Liang，et al. Recent advances in MOF-derived carbon-based nanomaterials for environmental applications in adsorption and catalytic degradation［J］. Chemical Engineering Journal，2022，427：131503. doi:10.1016/j.cej.2021.131503
3	BACELO H， PINTOR A M A， SANTOS S C R，et al. Performance and prospects of different adsorbents for phosphorus uptake and recovery from water［J］. Chemical Engineering Journal，2020，381：122566. doi:10.1016/j.cej.2019.122566
4	PINCUS L N， RUDEL H E， PETROVIĆ P V，et al. Exploring the mechanisms of selectivity for environmentally significant oxo-anion removal during water treatment：A review of common competing oxo-anions and tools for quantifying selective adsorption［J］. Environmental Science & Technology，2020，54（16）：9769-9790. doi:10.1021/acs.est.0c01666
5	ZHANG Peng， HE Mingming， HUO Silu，et al. Recent progress in metal-based composites toward adsorptive removal of phosphate：Mechanisms，behaviors，and prospects［J］. Chemical Engineering Journal，2022，446：137081. doi:10.1016/j.cej.2022.137081
6	HE Mingming， ZHANG Peng， ZHANG Xueli，et al. Efficient electro-assisted adsorption/desorption of phosphate on MOF-derived hierarchically porous carbon electrode［J］. Journal of Cleaner Production，2022，361：132262. doi:10.1016/j.jclepro.2022.132262
7	GAMAETHIRALALAGE J G， SINGH K， SAHIN S，et al. Recent advances in ion selectivity with capacitive deionization［J］. Energy & Environmental Science，2021，14（3）：1095-1120. doi:10.1039/d0ee03145c
8	TANG Kexin， HONG T Z X， YOU Liming，et al. Carbon-metal compound composite electrodes for capacitive deionization：Synthesis，development and applications［J］. 2019，7（47）：26693-26743. doi:10.1039/c9ta08663c
9	LIANG Hongxu， ZHANG Hongwei， WANG Qiang，et al. A novel glucose-based highly selective phosphate adsorbent［J］. Science of the Total Environment，2021，792：148452. doi:10.1016/j.scitotenv.2021.148452
10	NAZARIAN R， DESCH R J， THIEL S W. Kinetics and equilibrium adsorption of phosphate on lanthanum oxide supported on activated carbon［J］. Colloids and Surfaces A：Physicochemical and Engineering Aspects，2021，624：126813. doi:10.1016/j.colsurfa.2021.126813
11	GU Yifan， YANG Mengmeng， WANG Weili，et al. Phosphate adsorption from solution by zirconium-loaded carbon nanotubes in batch mode［J］. Journal of Chemical & Engineering Data，2019，64（6）：2849-2858. doi:10.1021/acs.jced.9b00214
12	LIU Ruiting， CHI Li’na， WANG Xinze，et al. Effective and selective adsorption of phosphate from aqueous solution via trivalent-metals-based amino-MIL-101 MOFs［J］. Chemical Engineering Journal，2019，357：159-168. doi:10.1016/j.cej.2018.09.122
13	LIU Ruiting， SHEN Jian， HE Xiaojuan，et al. Efficient macroporous adsorbent for phosphate removal based on hydrate aluminum-functionalized melamine sponge［J］. Chemical Engineering Journal，2021，421：127848. doi:10.1016/j.cej.2020.127848
14	LIU Ruiting， CHI Li’na， WANG Xinze，et al. Review of metal（hydr） oxide and other adsorptive materials for phosphate removal from water［J］. Journal of Environmental Chemical Engineering，2018，6（4）：5269-5286. doi:10.1016/j.jece.2018.08.008
15	HUO Silu， ZHAO Yubo， ZONG Mingzhu，et al. Boosting supercapacitor and capacitive deionization performance of hierarchically porous carbon by polar surface and structural engineering［J］. Journal of Materials Chemistry A，2020，8（5）：2505-2517. doi:10.1039/c9ta12170f
16	JU Xiaoqiu， HOU Jifei， TANG Yuqiong，et al. ZrO₂ nanoparticles confined in CMK-3 as highly effective sorbent for phosphate adsorption［J］. Microporous and Mesoporous Materials，2016，230：188-195. doi:10.1016/j.micromeso.2016.05.002
17	WANG Wenjuan， ZHOU Juan， WEI Dan，et al. ZrO₂-functionalized magnetic mesoporous SiO₂ as effective phosphate adsorbent［J］. Journal of Colloid and Interface Science，2013，407：442-449. doi:10.1016/j.jcis.2013.06.053
18	LIN Jianwei， HE Siqi， WANG Xingxing，et al. Removal of phosphate from aqueous solution by a novel Mg（OH）₂/ZrO₂ composite：Adsorption behavior and mechanism［J］. Colloids and Surfaces A：Physicochemical and Engineering Aspects，2019，561：301-314. doi:10.1016/j.colsurfa.2018.11.001
19	GUPTA N K， SAIFUDDIN M， KIM S，et al. Microscopic，spectroscopic，and experimental approach towards understanding the phosphate adsorption onto Zn-Fe layered double hydroxide［J］. Journal of Molecular Liquids，2020，297：111935. doi:10.1016/j.molliq.2019.111935
20	ZHANG Qian， JI Fangying， ZHAO Tiantao，et al. Systematic screening of layered double hydroxides for phosphate removal and mechanism insight［J］. Applied Clay Science，2019，174：159-169. doi:10.1016/j.clay.2019.03.030
21	FANG Liping， WU Baile， LO I M C. Fabrication of silica-free superparamagnetic ZrO₂@Fe₃O₄ with enhanced phosphate recovery from sewage：Performance and adsorption mechanism［J］. Chemical Engineering Journal，2017，319：258-267. doi:10.1016/j.cej.2017.03.012
22	WANG Ning， FENG Jiangtao， CHEN Jie，et al. Adsorption mechanism of phosphate by polyaniline/TiO₂ composite from wastewater［J］. Chemical Engineering Journal，2017，316：33-40. doi:10.1016/j.cej.2017.01.066
23	ZHU Enhao， HONG Xiaoting， YE Zhuoliang，et al. Influence of various experimental parameters on the capacitive removal of phosphate from aqueous solutions using LDHs/AC composite electrodes［J］. Separation and Purification Technology，2019，215：454-462. doi:10.1016/j.seppur.2019.01.004
24	ZHAO Yan， GUO Huixuan， HAN Hongguang，et al. Adsorptive behavior of prepared metal-organic framework composites on phosphates in aqueous solutions［J］. Adsorption Science & Technology，2021，2021：1-10. doi:10.1155/2021/6690361
25	HE Mingming， ZHANG Peng， HUO Silu，et al. Remarkable phosphate electrosorption/desorption by bimetallic MOF-derived hierarchically porous carbon electrode：In-situ creation of multiple active centers and boosting electrochemical activities［J］. Chemical Engineering Journal，2022，446：137396. doi:10.1016/j.cej.2022.137396
26	ZHANG Peng， HE Mingming， LI Fukuan，et al. Engineering bimetallic capture sites on hierarchically porous carbon electrode for efficient phosphate electrosorption：Multiple active centers and excellent electrochemical properties［J］. Journal of Materials Chemistry A，2023，11（2）：579-588. doi:10.1039/d2ta07752c
27	LIU Ruiting， CHI Li’na， FENG Jimeng，et al. MOFs-derived conductive structure for high-performance removal/release of phosphate as electrode material［J］. Water Research，2020，184：116198. doi:10.1016/j.watres.2020.116198

[1]	程一杰, 冯礼奎, 于志勇, 宋小宁, 安佳佳, 张晓松, 张大全. 电容去离子技术用于模拟调相机转子冷却水处理的研究[J]. 工业水处理, 2024, 44(10): 174-182.
[2]	陈卫, 胡文丽, 崔玉民. ZrO₂-CNB复合光催化剂的制备及其性能研究[J]. 工业水处理, 2023, 43(7): 113-119.
[3]	何立宁, 杜娟, 迟曼, 刘晓超. 新排放标准下伴生放射性废水处理工程设计[J]. 工业水处理, 2023, 43(3): 192-196.
[4]	刘倩,乔武宁,焦秀英,马元社. 换流阀均压电极电吸附抑垢方法研究[J]. 工业水处理, 2022, 42(12): 148-153.
[5]	董旭明, 张胜寒, 狄杰, 王智麟, 祁伟健. 电吸附电极材料的研究进展[J]. 工业水处理, 2022, 42(1): 48-55.
[6]	孙园,魏心雨,丁怡. 人工湿地在修复富营养化水体中的应用及研究进展[J]. 工业水处理, 2021, 41(2): 8-14.
[7]	方雨博,王趁义,汤唯唯,杨娜,王国贺,王凤玲. 除藻技术的优缺点比较、应用现状与新技术进展[J]. 工业水处理, 2020, 40(9): 1-6.
[8]	刘晓艳,王一楠,陆谢娟,陈才,吴晓晖,毛娟. CPC改性活性炭电极电吸附除砷性能研究[J]. 工业水处理, 2020, 40(2): 23-27.
[9]	牟祺,程国玲. Ti₃C₂层状电极电吸附去除水中铅离子研究[J]. 工业水处理, 2020, 40(10): 95-98.
[10]	魏永, 赵威, 石舟翔, 江晓栋, 姚维昊. ACF电吸附去除盐离子及其选择吸附性研究[J]. 工业水处理, 2018, 38(9): 37-40.
[11]	李谦, 刘志英, 许海辉, 赵宗锋, 徐炎华, 赵贤广. 负载Al₂O₃的活性炭纤维电吸附除盐研究[J]. 工业水处理, 2017, 37(9): 48-52.
[12]	张世春, 刘海宁, 王世栋, 崔香梅, 叶秀深. 电吸附电极制备研究进展[J]. 工业水处理, 2017, 37(5): 5-9.
[13]	王康, 程方, 尹晋. 炭纤维电极电吸附去除三氯酚的影响因素与机理[J]. 工业水处理, 2017, 37(12): 43-47.
[14]	刘江, 谢凤龙, 张鹏. 电吸附技术在电厂废水处理中的试验研究[J]. 工业水处理, 2015, 35(4): 68-71.
[15]	张建明. 电吸附除盐技术在某纺织集团的工程应用[J]. 工业水处理, 2015, 35(3): 100-102.

选择文件类型/文献管理软件名称

选择包含的内容