Hydrogen isotope separation at exceptionally high temperature using an unsaturated organometallic complex

被引：0

作者：

Kitayama, Taku ^{[1
]}

Yamauchi, Tamon ^{[1
]}

Uchida, Kaiji ^{[1
,2
]}

Tanaka, Shunya ^{[1
]}

Toyoda, Ryojun ^{[1
]}

Iguchi, Hiroaki ^{[1
]}

Sakamoto, Ryota ^{[1
]}

Xue, Hao ^{[1
]}

Kishimoto, Naoki ^{[1
]}

Yoshida, Takefumi ^{[3
]}

Uruga, Tomoya ^{[4
,5
]}

Noro, Shin-ichiro ^{[6
]}

Takaishi, Shinya ^{[1
,7
]}

机构：

[1] Tohoku Univ, Grad Sch Sci, Dept Chem, 6-3 Arama Ki Aza Aoba,Aoba Ku, Sendai 9808578, Japan

[2] Tokyo Metropolitan Ind Technol Res Inst, 2-4-10 Aomi, Tokyo 1350064, Japan

[3] Wakayama Univ, Grad Sch Syst Engn, Cluster Nanomat, 930 Sakaedani, Wakayama 6408510, Japan

[4] SPring 8, Japan Synchrotron Radiat Res Inst, Res & Utilizat Div, Sayo, Hyogo 6795198, Japan

[5] Univ Electrocommun, Innovat Res Ctr Fuel Cells, Chofu, Tokyo 1828585, Japan

[6] Hokkaido Univ, Fac Environm Earth Sci, Sapporo 0600810, Japan

[7] RIKEN, SPring 8 Ctr, Phys & Chem Res Infrastruct Grp, Sayo, Hyogo, Japan

来源：

DALTON TRANSACTIONS | 2025年 / 54卷 / 06期

基金：

日本科学技术振兴机构; 日本学术振兴会;

关键词：

MOLECULAR-ORBITAL METHODS; METAL-ORGANIC FRAMEWORK; ADSORBED SOLUTION THEORY; GAUSSIAN-TYPE BASIS; BASIS-SETS; DIHYDROGEN COMPLEXES; 3RD-ROW ATOMS; H-2; BINDING; DEUTERIUM; DESIGN;

D O I：

10.1039/d4dt03018d

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A new approach for hydrogen isotope separation using an unsaturated organometallic complex was proposed. Adsorption measurements of [Mn(dppe)2(CO)(N2)](BArF24) (Mn-dppe) (dppe = 1,2-bis(diphenylphosphino)ethane, BArF24 = B[C6H3(3,5-CF3)2]4) using H2 and D2 revealed a significant difference in the adsorption enthalpy of H2/D2 at much higher room temperatures than in previous studies, with D2 molecules being more strongly adsorbed on unsaturated metal sites. Mixed gas adsorption isotherms were calculated at each temperature using IAST, and it was predicted that D2 uptake was much larger than H2 uptake. Column chromatographic separation using the difference in adsorption enthalpy indicated that deuterium could be concentrated, and DFT calculations suggest that this difference in adsorption force is due to the difference in vibrational potentials involved in metal-dihydrogen bonding. This study introduces a new separation approach that could enable hydrogen isotope separation in the ambient temperature range.

引用

页码：2621 / 2627

页数：7

共 54 条

[1] Evaluation of the Thermodynamic Properties of H2 Binding in Solid State Dihydrogen Complexes [M(η2-H2)(CO)dppe2][BArF24] (M = Mn, Tc, Re): An Experimental and First Principles Study [J].

Abrecht, David G. ;

Fultz, Brent .

JOURNAL OF PHYSICAL CHEMISTRY C, 2012, 116 (42) :22245-22252

[2] HE-3 AND HE-4 FROM-D-2 ABSORBED IN LANI5 [J].

ADACHI, G ;

SAKAGUCHI, H ;

NAGAO, K .

JOURNAL OF ALLOYS AND COMPOUNDS, 1992, 181 :469-476

[3] Ortho-para equilibrium in a liquid D2 neutron moderator under irradiation -: art. no. 094114 [J].

Atchison, F ;

Beaud, P ;

Brys, T ;

Daum, M ;

Fierlinger, P ;

Henneck, R ;

Hofmann, T ;

Kirch, K ;

Kühne, G ;

Knopp, G ;

Pichlmaier, A ;

Serebrov, A ;

Spitzer, H ;

Wambach, J ;

Wimmer, J ;

Wokaun, A ;

Bodek, K ;

Geltenbort, P ;

Giersch, M ;

Zmeskal, J ;

Mishima, K .

PHYSICAL REVIEW B, 2003, 68 (09)

[4] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[5] Why does D-2 bind better than H-2? A theoretical and experimental study of the equilibrium isotope effect on H-2 binding in a M(eta(2)-H-2) complex. Normal coordinate analysis of W(CO)(3)(PCy3)(2)(eta(2)-H-2) [J].

Bender, BR ;

Kubas, GJ ;

Jones, LH ;

Swanson, BI ;

Eckert, J ;

Capps, KB ;

Hoff, CD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (39) :9179-9190

[6] Enhancement of D2/H2 Selectivity in Zeolite A through Partial Na-K Exchange: Single-Gas and Coadsorption Studies at 45-77 K [J].

Bezverkhyy, Igor ;

Giraudet, Maxence ;

Dirand, Celine ;

Macaud, Mathieu ;

Bellat, Jean-Pierre .

JOURNAL OF PHYSICAL CHEMISTRY C, 2020, 124 (45) :24756-24764

[7] COMPACT CONTRACTED BASIS-SETS FOR 3RD-ROW ATOMS - GA-KR [J].

BINNING, RC ;

CURTISS, LA .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 1990, 11 (10) :1206-1216

[8] Extension of Gaussian-2 (G2) theory to molecules containing third-row atoms K and Ca [J].

Blaudeau, JP ;

McGrath, MP ;

Curtiss, LA ;

Radom, L .

JOURNAL OF CHEMICAL PHYSICS, 1997, 107 (13) :5016-5021

[9] Measurements of the Neutron Cross Sections of Hydrogen and Deuterium in H2O-D2O Mixtures Using the Deep Inelastic Neutron-Scattering Technique [J].

Blostein, J. J. ;

Palomino, L. A. Rodriguez ;

Dawidowski, J. .

PHYSICAL REVIEW LETTERS, 2009, 102 (09)

[10] Quantum sieving: feasibility and challenges for the separation of hydrogen isotopes in nanoporous materials [J].

Cai, Jinjun ;

Xing, Yanlong ;

Zhao, Xuebo .

RSC ADVANCES, 2012, 2 (23) :8579-8586

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