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 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]

图2 （a）不同孔径的多孔材料的D2/H2分离性能对比[20]（1 bar=0.1 MPa）；（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 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]

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、不同压力下的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) 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]

图4 （a）MOF-74-IMs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）不同温度下MOF-74-ac和MOF-74-IMs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 酸（a）和碱（b）催化合成氢同位素标记化合物[50-51]

Fig.5 Acid (a) and base (b) 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 with dimetallacylic intermediates （a） and with monometallacy intermediates (b)[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H2异裂解产生的氢化物和质子进行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]