为实现农业废弃物油菜籽渣的高值化利用并解决放射性碘的高效捕获难题,本文以油菜籽渣为前驱体,经水热-碱活化制备多孔活性炭载体,并采用溶剂热法构筑不同铋负载量的复合材料(Bi/RS),结合扫描电子显微镜、透射电子显微镜、X射线衍射仪、X射线光电子能谱仪等分析复合材料的微观结构,并通过气相碘、碘/环己烷溶液及碘水溶液吸附实验,系统探究其吸附动力学及吸附机理。结果表明：纳米铋(Bi0)均匀分散于碳骨架表面及孔道中,使得材料的比表面积略微减小,但仍保持发达的微孔结构;铋的引入显著增强了复合材料的化学固碘能力,Bi/RS-0.4在气相吸附中循环3次后的碘保留率高达83.1%;在液相吸附中,低负载量的Bi/RS-0.1表现最佳,对碘/环己烷溶液去除率超99%,在碘水溶液中的饱和吸附量高达 2 293 mg/g。物理吸附(孔道截留)与化学吸附(Bi-I沉淀及官能团络合)的协同作用是Bi/RS能高效固碘的关键。Bi/RS不仅实现了废弃油菜籽渣的资源化利用,且在气液两相中均具有优异的吸附性能与稳定性,为放射性碘废物的治理提供了理论与材料基础。
To achieve high-value utilization of agricultural waste rapeseed residue and address the challenge of efficient radioactive iodine capture, this study utilized rapeseed residue as a precursor to prepare porous activated carbon carriers via hydrothermal-alkali activation. Subsequently, a solvothermal method was employed to construct composites (Bi/RS) with varying bismuth loadings. The microstructure of composites were analyzed by combining scanning electron microscope, transmission electron microscope, X-ray diffractometer, X-ray photoelectron spectrometer, etc. Adsorption experiments using gaseous iodine, iodine/cyclohexane solution, and aqueous iodine solution were conducted to systematically investigate the adsorption kinetics and mechanism. Results indicate that nanoscale bismuth (Bi0) is uniformly dispersed on the carbon framework surface and within its pores, slightly reducing the specific surface area of materials while maintaining a highly developed micropore structure. The incorporation of bismuth significantly enhances chemical iodine fixation capacity of composites, with Bi/RS-0.4 achieving an iodine retention rate of 83.1% after three adsorption cycles in the gas phase adsorption. In liquid phase adsorption, the low-loading Bi/RS-0.1 exhibit optimal performance, achieving over 99% removal efficiency for iodine/cyclohexane solutions and a saturated adsorption capacity of 2 293 mg/g in aqueous iodine solutions. The synergistic effect of physical adsorption (pore trapping) and chemical adsorption (Bi-I precipitation and functional group complexation) is key to efficient iodine fixation of Bi/RS. Bi/RS not only achieves resource utilization of waste rapeseed residue but also exhibits outstanding adsorption performance and stability in both gas and liquid phases, providing a theoretical and material foundation for radioactive iodine waste management.
[1] IMAM E A, EL-SAYED I E, MAHFOUZ M G, et al. Synthesis of α-aminophosphonate functionalized chitosan sorbents: effect of methyl vs phenyl group on uranium sorption[J]. Chemical Engineering Journal, 2018, 352: 1022-1034.
[2] XIE Y, CHEN C L, REN X M, et al.Emerging natural and tailored materials for uranium-contaminated water treatment and environmental remediation[J]. Progress in Materials Science, 2019, 103: 180-234.
[3] AZAMBRE B, CHEBBI M.Evaluation of silver zeolites sorbents toward their ability to promote stable CH3I storage as AgI precipitates[J]. ACS Applied Materials & Interfaces, 2017, 9(30): 25194-25203.
[4] MATYÁŠ J, ILTON E S, KOVAŘÍK L. Silver-functionalized silica aerogel: towards an understanding of aging on iodine sorption performance[J]. RSC Advances, 2018, 8(56): 31843-31852.
[5] CHEN P, HE X H, PANG M B, et al.Iodine capture using Zr-based metal-organic frameworks (Zr-MOFs): adsorption performance and mechanism[J]. ACS Applied Materials & Interfaces, 2020, 12(18): 20429-20439.
[6] ZHANG X R, MADDOCK J, NENOFF T M, et al.Adsorption of iodine in metal-organic framework materials[J]. Chemical Society Reviews, 2022, 51(8): 3243-3262.
[7] 周雨奇, 喻吉, 陈洋, 等. 农业废弃物稻壳合成SiC和Si3N4/SiC纳米粉体的研究进展[J]. 粉末冶金材料科学与工程, 2026, 31(1): 24-36.
ZHOU Yuqi, YU Ji, CHEN Yang, et al.Research progress on synthesis of SiC and Si3N4/SiC nanopowders from agricultural waste rice husk[J]. Materials Science and Engineering of Powder Metallurgy, 2026, 31(1): 24-36.
[8] MA J C, XU S P, WANG X T, et al.Biomass derived porous carbon for efficient iodine adsorption from vapor and solution[J]. Separation and Purification Technology, 2024, 347: 127613.
[9] PENG L, DUAN J L, LIANG Y, et al.Recent advances in metal-organic frameworks and their derivatives for adsorption of radioactive iodine[J]. Molecules, 2024, 29(17): 4170.
[10] SHEN Z H, WIECHERT A I, CHOI S, et al.Silver-functionalized silica aerogel for iodine capture: adsorbent aging by NO2 in spent nuclear fuel reprocessing off-gas[J]. Microporous and Mesoporous Materials, 2022, 336: 111898.
[11] HAO Y X, TIAN Z J, LIU C Y, et al.Recent advances in the removal of radioactive iodine by bismuth-based materials[J]. Frontiers in Chemistry, 2023, 11: 1122484.
[12] REDA A T, PAN M, ZHANG D X, et al.Bismuth-based materials for iodine capture and storage: a review[J]. Journal of Environmental Chemical Engineering, 2021, 9(4): 105279.
[13] YANG J H, SHIN J M, PARK J J, et al.Novel synthesis of bismuth-based adsorbents for the removal of 129I in off-gas[J]. Journal of Nuclear Materials, 2015, 457: 1-8.
[14] KWAK J, LEE S H, SHIN J, et al.Synthesis and applications of bismuth-impregnated biochars originated from spent coffee grounds for efficient adsorption of radioactive iodine: a mechanism study[J]. Environmental Pollution, 2022, 313: 120138.
[15] ZOU H, DONG H L, YOU W J, et al.Bismuth-embedded columnar activated carbon for gaseous radiodine capture[J]. Materials Science and Engineering B, 2025, 317: 118186.
[16] IANĂŞI C, SVERA P, POPA A, et al. Adsorbent material based on carbon black and bismuth with tunable properties for gold recovery[J]. Materials, 2023, 16(7): 2837.
[17] YAN H, JIANG X, XIA H Y, et al.Preparation of bismuth-activated carbon and application to methylene orange removal[J]. Desalination and Water Treatment, 2021, 230: 372-383.
[18] 许伟, 刘军利, 应浩, 等. 磷酸活化提升丁烷工作容量并制备高性能汽车碳罐用活性炭[J]. 环境工程学报, 2021, 15(6): 1946-1955.
XU Wei, LIU Junli, YING Hao, et al.Preparation of activated carbon with high butane work capacity for automobile carbon canister by phosphoric acid activation[J]. Chinese Journal of Environmental Engineering, 2021, 15(6): 1946-1955.
[19] LIU B Y, MAO C C, ZHOU Z A, et al.Two facile aniline-based hypercrosslinked polymer adsorbents for highly efficient iodine capture and removal[J]. International Journal of Molecular Sciences, 2023, 24(1): 370.
[20] ZHU H, CAO L Y, CHENG X, et al.In-site interface growth of bismuth-based hydrothermal carbon using collagen fiber for selective removal of iodide ion from wastewater[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2023, 664: 131177.
[21] JEFFERY G H, BASSETT J, DENNEY R C.Vogel's Textbook of Quantitative Chemical Analysis: Fifth Edition[M]. New York: John Wiley & Sons, Icn., 1989.
[22] LI Y H, LV K L, HO W, et al.Enhanced visible-light photo-oxidation of nitric oxide using bismuth-coupled graphitic carbon nitride composite heterostructures[J]. Chinese Journal of Catalysis, 2017, 38(2): 321-329.
[23] GUO J L, WANG X L, MIAO P L, et al.One-step seeding growth of controllable Ag@Ni core-shell nanoparticles on skin collagen fiber with introduction of plant tannin and their application in high-performance microwave absorption[J]. Journal of Materials Chemistry, 2012, 22(24): 11933.
[24] ZHU H, WANG B, ZHU W K, et al.Space and structure activation of collagen fiber for high efficient capture iodine in off-gas[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 617: 126389.
[25] XIAN Q, CHEN L, FAN W J, et al.Facile synthesis of novel Bi0-SBA-15 adsorbents by an improved impregnation reduction method for highly efficient capture of iodine gas[J]. Journal of Hazardous Materials, 2022, 424: 127678.
[26] WANG E C, CHEN L, HE X M, et al.Capture of iodine gas by Bi-based composites derived from rice husk: influence of the type of support on the iodine adsorption and retention[J]. Chemical Engineering Journal, 2023, 465: 143069.
[27] JUNG Y E, KANG S W, YIM M S.Feasibility study of using Bi-mna metal-organic frameworks as adsorbents for radioiodine capture at high temperature[J]. Industrial & Engineering Chemistry Research, 2021, 60(16): 5964-5975.
[28] TIAN Z J, CHEE T S, ZHU L, et al.Comprehensive comparison of bismuth and silver functionalized nickel foam composites in capturing radioactive gaseous iodine[J]. Journal of Hazardous materials, 2021, 417: 125978.
