Advances in light isotopes separation and catalytic labeling

doi:10.11949/0438-1157.20231277

Abstract

Abstract:

Stable light isotopes such as hydrogen, carbon, nitrogen and oxygen are widely used in medical drugs, clinical diagnosis, environmental geology and other fields. 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

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吸附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出应用潜力；而催化同位素交换法和官能团转化法是制备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

CLC Number:

TB 34

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, 2024, 75(4): 1284-1301.

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, 2024, 75(4): 1284-1301.

Figures/Tables 8

Fig.1 (a) Transport diffusivity of H2 and D2 under different temperature (insets show the one α cage of RHO zeolite 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]

Fig.2 (a) Comparison of the D2/H2 molar 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 of 18O2/16O2 at 112 K[30]

Fig.3 (a) TDS spectra of CPO-27-Co for pure gas H2 (open black circle) and D2 (filled red circle); (b) 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) Selectivities of D2/H2 for Cu(Ⅰ)-ZSM-5 at the temperature range of 23—273 K[37]

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]

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

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

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]

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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