氢化石墨炔对甲基汞的去除性能及机制研究

摘要
图/表
参考文献
相关文章 (15)

全文: PDF (2610 KB) HTML (1 KB)
输出: BibTeX | EndNote (RIS)

摘要以三乙炔基苯为前驱体通过原位交叉偶联反应合成了氢化石墨炔(HsGDY),对比研究了新型sp杂化碳材料HsGDY与代表性传统sp²杂化碳材料石墨烯(GE)的CH₃Hg⁺吸附性能,探究了溶液pH值、投加量、离子强度、共存Hg²⁺等条件对HsGDY的CH₃Hg⁺吸附性能的影响规律,揭示了HsGDY对CH₃Hg⁺的吸附脱除机制.HsGDY对CH₃Hg⁺具有优良的吸附去除能力,明显优于GE.当HsGDY投加量为30mg,溶液pH=7,1.25 μg/L CH₃Hg⁺浓度条件下,HsGDY对CH₃Hg⁺的最终去除效率可以接近100%.由于竞争吸附,离子强度增加,pH降低及共存Hg²⁺会一定程度上抑制HsGDY对CH₃Hg⁺的吸附.HsGDY具有良好的再生及重复利用性能,经过5次再生其CH₃Hg⁺吸附去除效率仍可达到80%以上.结合拉曼光谱(Raman)、红外光谱(FTIR)、X射线光电子能谱(XPS)等表征方法以及密度泛函理论(DFT)计算,深入研究了HsGDY对CH₃Hg⁺的吸附脱除机制.结果表明,HsGDY对CH₃Hg⁺的吸附为表面化学吸附,主要源自其炔键官能团与CH₃Hg⁺间的相互作用.

	服务

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	E-mail Alert
	RSS
	作者相关文章
	李鸿鹄
	鲁华英
	彭喜燕
	沈振华
	安淼
	揭翠
	杨娇羽

关键词 ：氢化石墨炔, 甲基汞, sp杂化碳, 炔键

Abstract：Hydrogen substituted graphdiyne (HsGDY) was synthesized through an in-situ cross-coupling reaction with triethynylbenzene as a precursor. The CH₃Hg⁺adsorption performance of the novel sp-hybridized carbon material HsGDY was studied in comparison with traditional sp²-hybridized carbon material graphene (GE). This work showed that HsGDY had an excellent adsorption performance for CH₃Hg⁺, which was significantly better than GE. When the CH₃Hg⁺ concentration was 1.25 μg/L and solution pH was 7, the final removal efficiency of HsGDY with 30 mg dosage for CH₃Hg⁺ could reach nearly 100%. An increase in ion strength, a decrease in pH and the presence of Hg²⁺ would to some extent inhibit the adsorption of CH₃Hg⁺ on HsGDY due to the competitive adsorption effect. HsGDY had good regeneration performance. After 5 regeneration cycles, its CH₃Hg⁺removal efficiency was still above 80%. By characterization methods such as Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations, the adsorption mechanism of CH₃Hg⁺ onto HsGDY was thoroughly studied. The results indicated that CH₃Hg⁺ was chemically adsorbed on the HsGDY surface, mainly due to the interaction between the acetylenic functional group and CH₃Hg⁺.

Key words： hydrogen substituted graphdiyne methylmercury sp-hybridized carbon acetylene bond

收稿日期: 2024-05-14

PACS:

X703.5

基金资助:国家自然科学基金青年基金资助项目(52100134);中南财经政法大学中央高校基本科研业务费专项资金资助项目(2722024EJ024);中国博士后科学基金资助面上项目(2022M721284)

通讯作者: 李鸿鹄,副教授,lhhsam@outlook.com E-mail: lhhsam@outlook.com

作者简介: 李鸿鹄(1991-),男,湖北京山人,副教授,博士,主要研究方向为烟气污染物治理.发表论文30余篇.lhhsam@outlook.com.

引用本文:

李鸿鹄, 鲁华英, 彭喜燕, 沈振华, 安淼, 揭翠, 杨娇羽. 氢化石墨炔对甲基汞的去除性能及机制研究[J]. 中国环境科学, 2025, 45(1): 198-207. LI Hong-hu, LU Hua-ying, PENG Xi-yan, SHEN Zhen-hua, AN Miao, JIE Cui, YANG Jiao-yv. Study on the performance and mechanism of methylmercury removal by hydrogen substituted graphdiyne. CHINA ENVIRONMENTAL SCIENCECE, 2025, 45(1): 198-207.

链接本文:

http://www.zghjkx.com.cn/CN/ 或 http://www.zghjkx.com.cn/CN/Y2025/V45/I1/198

[1] Li B Y, Zhang Y M, Ma D X, et al. Mercury nano-trap for effective and efficient removal of mercury(II) from aqueous solution [J]. Nature communications, 2014,5:5537.
[2] Lyu H, Xia S, Tang J, et al. Thiol-modified biochar synthesized by a facile ball-milling method for enhanced sorption of inorganic Hg²⁺and organic CH₃Hg⁺[J]. Journal of Hazardous Materials, 2020,384: 121357.
[3] Huang Y, Tang J C, Gai L S, et al. Different approaches for preparing a novel thiol-functionalized graphene oxide/Fe-Mn and its application for aqueous methylmercury removal [J]. Chemical Engineering Journal, 2017,319:229-239.
[4] O'Connor D, Hou D Y, Ok Y S, et al. Mercury speciation, transformation, and transportation in soils, atmospheric flux, and implications for risk management: a critical review [J]. Environment International, 2019,126:747-761.
[5] Pei P G, Xu Y M, Wang L, et al. Thiol-functionalized montmorillonite prepared by one-step mechanochemical grafting and its adsorption performance for mercury and methylmercury [J]. Science of the Total Environment, 2022,806:150510.
[6] Li Y M, Chen L, Liang S, et al. Looping mercury cycle in global environmental-economic system modeling [J]. Environmental Science & Technology, 2022,56:2861-2879.
[7] Mercury and health. https://www.who.int/news-room/fact-sheets/detail/mercury-and-health.
[8] Zhao L, Zhang Y R, Wang L, et al. Effective removal of Hg(II) and MeHg from aqueous environment by ball milling aided thiol- modification of biochars: Effect of different pyrolysis temperatures [J]. Chemosphere, 2022,294:133820.
[9] Tipping E. Modelling the interactions of Hg (II) and methylmercury with humic substances using WHAM/Model VI [J]. Applied geochemistry, 2007,22:1624-1635.
[10] Krishna Kumar A S, Jiang S J, Tseng W L. Facile synthesis and characterization of thiol-functionalized graphene oxide as effective adsorbent for Hg(II) [J]. Journal of Environmental Chemical Engineering, 2016,4:2052-2065.
[11] 谢童,薛炳松,王珊,等.巯基改性生物炭对水中甲基汞的吸附 [J]. 农业环境科学学报, 2022,41(1):162-170. Xie T, Xue B S, Wang S, et al. Methylmercury adsorption characteristics of thiol-modified biochar in water [J]. Journal of Agro-Environment Science, 2022,41(1):162-170.
[12] Li Y J, Li W F, Liu Q N, et al. Alkynyl carbon materials as novel and efficient sorbents for the adsorption of mercury (II) from wastewater [J]. Journal of Environmental Sciences, 2018,68:169-176.
[13] Zheng X L, Gao X, Vilá R A, et al. Hydrogen-substituted graphdiyne- assisted ultrafast sparking synthesis of metastable nanomaterials [J]. Nature Nanotechnology, 2023,18:153-159.
[14] Ren X, Li X D, Yang Z, et al. Tailoring acetylenic bonds in graphdiyne for advanced lithium storage [J]. ACS Sustainable Chemistry & Engineering, 2020,8:2614-2621.
[15] He J J, Wang N, Cui Z L, et al. Hydrogen substituted graphdiyne as carbon-rich flexible electrode for lithium and sodium ion batteries [J]. Nature communications, 2017,8:1172.
[16] Crini G, Badot P M. Application of chitosan, a natural aminopolysaccharide, for dye removal from aqueous solutions by adsorption processes using batch studies: a review of recent literature [J]. Progress in Polymer Science, 2008,33:399-447.
[17] Muller K A, Brandt C C, Mathews T J, et al. Methylmercury sorption onto engineered materials [J]. Journal of Environmental Management, 2019,245:481-488.
[18] Tuzen M, Sarı A, Mogaddam M R A, et al. Synthesis of carbon modified with polymer of diethylenetriamine and trimesoyl chloride for the dual removal of Hg (II) and methyl mercury ([CH₃Hg]⁺) from wastewater: Theoretical and experimental analyses [J]. Materials Chemistry and Physics, 2022,277:125501.
[19] 刘朝淑,莫雅斐,孙荣国,等.水华束丝藻和铜绿微囊藻对水中甲基汞的吸附特征及动力学研究 [J]. 地球与环境, 2020,48(4):518-524. Liu X S, Mo Y F, Sun R G, et al. Study on adsorption characteristics and kinetics of methylmercury in water by aphanizomenon flosaquae and microcystis aeruginosa [J]. Earth and Environment, 2022,48(4): 518-524.
[20] 党娅琴,邢英.稻壳生物炭吸附无机汞和甲基汞的特征研究 [J]. 地球与环境, 2022,50(5):666-675. Dang Y Q, Xing Y. The characteristic of adsorption of inorganic mercury and methylmercury by rice husk biochar [J]. Earth and Environment, 2022,50(5):666-675.
[21] Saman N, Johari K, Song S T, et al. High removal efficiency of Hg(II) and MeHg(II) from aqueous solution by coconut pith—Equilibrium, kinetic and mechanism analyses [J]. Journal of Environmental Chemical Engineering, 2016,4:2487-2499.
[22] Huang Y, Gong Y Y, Tang J C, et al. Eﬀective removal of inorganic mercury and methylmercury from aqueous solution using novel thiol-functionalized graphene oxide/Fe-Mn composite [J]. Journal of Hazardous Materials, 2019,366:130-139.
[23] Huang Y, Xia S Y, Lyu J J, et al. Highly efcient removal of aqueous Hg²⁺ and CH₃Hg⁺ by selective modifcation of biochar with 3-mercaptopropyltrimethoxysilane [J]. Chemical Engineering Journal, 2019,360:1646-1655.
[24] Li G Z, Liu M, Zhang Z Q, et al. Extraction of methylmercury and ethylmercury from aqueous solution using surface sulfhydryl- functionalized magnetic mesoporous silica nanoparticles [J]. Journal of Colloid and Interface Science, 2014,424:124-131.
[25] Say R, Birlik E, Erdemgil Z, et al. Removal of mercury species with dithiocarbamate-anchored polymer/organosmectite composites [J]. Journal of Hazardous Materials, 2008,150:560-564.
[26] Kushwaha S, Sreedhar B, Padmaja P, et al. Sorption of Phenyl Mercury, Methyl Mercury, and Inorganic Mercury onto Chitosan and Barbital Immobilized Chitosan: Spectroscopic, Potentiometric, Kinetic, Equilibrium, and Selective Desorption Studies [J]. Journal of Chemical and Engineering Data, 2010,55(11):4691-4698.
[27] Li S X, Zheng F Y, Huang Y, et al. Thorough removal of inorganic and organic mercury from aqueous solutions by adsorption on Lemna minor powder [J]. Journal of Hazardous Materials, 2011,186(1):423- 429.
[28] D Karunasagar, M V Balarama Krishna, et al. Removal and preconcentration of inorganic and methyl mercury from aqueous media using a sorbent prepared from the plant Coriandrum sativum [J]. Hazard Mater, 2005,118:133-139.