轻同位素分离纯化与催化标记研究进展

doi:10.11949/0438-1157.20231277

摘要/Abstract

摘要：

氢碳氮氧等稳定轻同位素广泛应用于医疗药物、临床诊断、环境地质等领域。如何获得高纯同位素原料并将其标记到目标化合物是同位素产业的核心技术。基于量子效应的同位素分离方法具有选择性高、能耗低等优势，在同位素分离纯化方面展现应用潜力；而催化同位素交换法和官能团转化法是实现同位素标记化合物的重要手段。基于量子效应的同位素分离与催化标记技术的核心之一是开发高效吸附及催化材料。总结了同位素分离及标记的最新进展，分析了核心材料的发展现状与性能强化方法，并对轻同位素分离纯化及标记方面的挑战和发展趋势进行了展望。

关键词: 同位素分离, 量子效应, 吸附剂, 同位素标记, 多孔材料, 催化剂

Abstract:

Stable isotopes of the light elements (H, C, N, O, etc) are widely used in numerous physical and chemical processes for medical drugs, clinical diagnosis, environment, and geology. The enrichment of high-purity isotopes as raw materials to obtain targeted isotope-labeled compounds are core technology for isotope application. Adsorption separation based on quantum effect displays low energy footprint and high efficiency and thus is considered as a promising method for the purification of isotope gases. Catalytic isotope exchange and functional group conversion reactions are important technologies for isotope labeling. The key for both processes is the development of efficient adsorbents and catalysts. This paper summarizes the recent research progress for isotopes separation and catalytic labeling. Then, the development status of key materials is analyzed along with the strategy for performance optimization. Finally, the research challenges and developing trends in this field are prospected.

Key words: isotope separation, quantum effect, adsorbents, isotope labeling, porous materials, catalysts

中图分类号:

TB34

李添翼, 武玉泰, 王永胜, 顾佳锐, 宋沂恒, 杨丰铖, 郝广平. 轻同位素分离纯化与催化标记研究进展[J]. 化工学报, DOI: 10.11949/0438-1157.20231277.

Tianyi LI, Yutai WU, Yongsheng WANG, Jiarui GU, Yiheng SONG, Fengcheng YANG, Guangping HAO. Advances in light isotopes separation and catalytic labeling[J]. CIESC Journal, DOI: 10.11949/0438-1157.20231277.

图/表 8

图1 (a) 不同温度下H2和D2在RHO分子筛中的扩散速率对比，插图：RHO分子筛的α笼以及连接两个笼之间的8元环孔道[14]；(b) 量子效应下H2和D2不同有效直径的示意图[17]

Fig.1(a) Transport diffusivity of H2 and D2 under different temperature, insets show the one α cage of zeolite RHO and the 8-ring window of RHO zeolites connecting two cages[14]; (b) Schematic representation for the different effective size of H2 and D2 under quantum effect[17]

图2 (a) 不同孔径的多孔材料的D2/H2分离性能对比[20]；(b) 在MIL-53的一维孔道中利用呼吸效应分离D2/H2的示意图[25]；(c) DUT-8的H2与D2的吸附等温线[27]；(d) 碳化物衍生碳的孔道3D示意图，不同颜色的球代表不同尺寸的孔；(e) 112 K下不同孔尺寸及构型的18O2/16O2选择性对比[30]

Fig.2(a) Comparison of the molar D2/H2 ratio as function of the effective pore size of organic frameworks over a temperature range[20]; (b) Schematic view of D2 separation in 1D channel of MIL-53 (Al) during the breathing propagation[25]; (c) H2 and D2 isotherms for DUT-8(Ni) at 20.3 and 23.3 K[27]; (d) 3D rendering of the same slice filled with nonoverlapping spheres. The spheres are colored by diameter, with the values indicated in the color bar; (e) Pore geometry-dependent selectivity S at 1% pore volume filling at 112 K[30]

图3(a) CPO-27-Co对D2和H2的TDS实验图谱，插图表示其对应的吸附位点；(b) CPO-27-Co在不同温度下的D2/H2吸附选择性[35]；(c) Cu(I)-ZSM-5在60 K吸附后的TDS图谱；(d) 不同温度下Cu(I)-ZSM-5的D2/H2的选择性[37]

Fig.3 (a) TDS spectra of CPO-27-Co for pure gas H2 (open black circle) and D2 (filled red circle); (b) The selectivities of D2/H2 for CPO-27-Co at the temperature range of 19.5-70 K and pressure range of 0-1 bar[35]; (c) TDS spectra of Cu(I)-ZSM-5 for pure gas H2 and D2; (d) The selectivities of D2/H2 for Cu(I)-ZSM-5 at the temperature range of 23-273 K[37]

图4 (a) MOF-74-IM协同效应分离示意图，其中，开放金属位点作为CAQS位点，咪唑(IM)修饰的狭窄孔道作为KQS位点；(b) 不同量IM修饰孔道后的MOF-74对D2/H2的选择性[39]；(c) 同位素膜法分离装置示意图[43]；(d) H+和D+在透过单层六方氮化硼时的伏安曲线[42]

Fig.4 (a) Illustration of the CAQS and KQS sites in MOF-74-IMs; (b) Selectivity of MOF-74-ac and MOF-74-IMs as a function of exposure temperature[39]; (c) Illustration of selective proton pumping through a graphene sandwich membrane-electrode assembly[43]; (d) Examples of I-V characteristics for H+/D+ transport through monolayers of hBN[42]

图5 (a) 酸和 (b) 碱催化合成氢同位素标记化合物[50-51]

Fig.5 (a) Acid and (b) base catalyzed synthesis of hydrogen isotope labelling compound[50-51]

图6 Ru纳米催化剂对N-杂环化合物进行氘标记的一般机制途径：(a)使用双金属环中间体, (b)单金属环中间体[61]

Fig. 6 General mechanistic pathway for the deuterium labeling of N-heterocyclic compounds using Ru NPs (a) with dimetallacylic intermediates and (b) with monometallacy intermediates[61]

图7 (a) Ru/C和NHC修饰的Ru/C催化剂对不同醛类化合物中甲酰基官能团的氘标记性能对比[63]；(b) 炭载铁基催化剂催化HIE反应可能的机理途径[64]；(c) 顺式烯烃与块材金属或单原子分散的金属表面上对H2异裂解离产生的氢化物和质子后进行H/D交换反应示意图[65]；(d) Pt/CeO2-D2O无H2体系氘标记苯胺的可能反应路径[69]

Fig. 7 (a) Comparison of the deuterium labeling performance for formyl group in various aldehydes using Ru/C and NHC-modified Ru/C catalysts [63]; (b) Possible mechanistic pathways for the catalytic HIE using carbon-supported iron[64]; (c) Schematic illustration of the H/D exchange and reaction of cis-alkene with active H atoms on block metal surface or with hydride and proton derive from the heterolytic dissociation of H2 on atomically dispersed metal catalysts[65]; (d) Possible reaction pathways for the deuteration of aniline in a Pt/CeO2-D2O system without H2[69]

图8 (a) 半导体光催化剂上电子和空穴的协同作用实现可控同位素标记的N-甲基化胺的合成[80]；(b) 多孔CdSe光催化剂催化C-X到C-D转化的自由基途径[83]；(c) 铜纳米线阵列电催化剂脱卤氘代反应的机制[85]；(d) 钯膜反应器的氘化反应步骤示意图[93]

Fig. 8 (a) Mechanistic proposal of the controllable isotope-labeled N-methylation of amines by the synergistic utilization of electrons and holes on a semiconductor photocatalyst[80]; (b) Porous CdSe photocatalyst catalyzes the radical pathway for C-X to C-D transformation[83]; (c) Mechanism of dehalogenation deuteration reaction of Cu nanowires array electrocatalysts[85]; (d) Schematic diagram of the deuteration reaction steps for the palladium membrane reactor[93]

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