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Title: The structure and unconventional dihydrogen bonding of a pressure-stabilized hydrogen-rich (NH 3 BH 3 )(H 2 ) x (x = 1.5) compound

Authors:
ORCiD logo; ORCiD logo; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1352254
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Materials Chemistry. A; Journal Volume: 5; Journal Issue: 15
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Lin, Yu, Welchman, Evan, Thonhauser, Timo, and Mao, Wendy L. The structure and unconventional dihydrogen bonding of a pressure-stabilized hydrogen-rich (NH 3 BH 3 )(H 2 ) x (x = 1.5) compound. United States: N. p., 2017. Web. doi:10.1039/C7TA01005B.
Lin, Yu, Welchman, Evan, Thonhauser, Timo, & Mao, Wendy L. The structure and unconventional dihydrogen bonding of a pressure-stabilized hydrogen-rich (NH 3 BH 3 )(H 2 ) x (x = 1.5) compound. United States. doi:10.1039/C7TA01005B.
Lin, Yu, Welchman, Evan, Thonhauser, Timo, and Mao, Wendy L. Sun . "The structure and unconventional dihydrogen bonding of a pressure-stabilized hydrogen-rich (NH 3 BH 3 )(H 2 ) x (x = 1.5) compound". United States. doi:10.1039/C7TA01005B.
@article{osti_1352254,
title = {The structure and unconventional dihydrogen bonding of a pressure-stabilized hydrogen-rich (NH 3 BH 3 )(H 2 ) x (x = 1.5) compound},
author = {Lin, Yu and Welchman, Evan and Thonhauser, Timo and Mao, Wendy L.},
abstractNote = {},
doi = {10.1039/C7TA01005B},
journal = {Journal of Materials Chemistry. A},
number = 15,
volume = 5,
place = {United States},
year = {Sun Jan 01 00:00:00 EST 2017},
month = {Sun Jan 01 00:00:00 EST 2017}
}
  • Combining X-ray diffraction, Raman spectroscopy, and ab initio simulations we characterize an extremely hydrogen-rich phase with the chemical formula (NH 3BH 3)(H 2) x (x = 1.5). This phase was formed by compressing ammonia borane (AB, NH 3BH 3) in an environment with an excess of molecular hydrogen (H 2). This compound can store a total of 26.8 wt% hydrogen, both as molecular hydrogen and chemically bonded hydrogen in AB, making it one of the most hydrogen-rich solids currently known. The new compound possesses a layered AB structure where additional H 2 molecules reside in channels created through the weavingmore » of AB layers. The unconventional dihydrogen bonding network of the new compound is significantly modified from its parent AB phase and contains H•••H contacts between adjacent AB molecules and between AB and H 2 molecules. H–H can be either a proton donor or a proton acceptor that forms new types of dihydrogen bonding with the host AB molecules, which are depicted as H–H•••H–B or H–H•••H–N, respectively. Furthermore, this study not only demonstrates the strategy and the promise of using pressure for new material synthesis, but also unleashes the power of combining experiments and ab initio calculations for elucidating novel structures and unusual bonding configurations in dense low-Z materials.« less
  • Boraneamines tend to have close N-H{sup {delta}+}{hor{underscore}ellipsis}{sup {delta}{minus}}H-B contacts as a result of the intermolecular interaction of the NH proton with the BH bond by a novel type of hydrogen bond (the dihydrogen bond). A CSD structural search provides characteristic metric data for the interaction: the H{hor{underscore}ellipsis}H distance is in the range 1.7--2.2 {angstrom}, and the N-H{hor{underscore}ellipsis}H group tends to be linear while B-H{hor{underscore}ellipsis}H tends to be bent. The reported X-ray structure of BH{sub 3}NH{sub 3} seemed to provide a singular exception in having bent N-H{hor{underscore}ellipsis}H and linear B-H{hor{underscore}ellipsis}H. Neutron diffraction structure of BH{sub 3}NH{sub 3} now shows that themore » B and N atoms must be reversed from the assignment previously published. With the correct assignment the authors find the expected bent B-H{hor{underscore}ellipsis}H and linear N-H{hor{underscore}ellipsis}H arrangement in the closest intermolecular N-H{hor{underscore}ellipsis}H-B interaction (d{sub HH} = 2.02 {angstrom}).« less
  • The first microporous solids incorporating two octahedrally coordinated transition elements, the phosphates (TMA)[sub 2](NH[sub 4])[sub 2][Fe[sub 2]Mo[sub 12]O[sub 30](H[sub 2]PO[sub 4])[sub 6](HOP[sub 4])[sub 2]][center dot]11H[sub 2]O (1) and (TMA)[sub 2]Na[sub 4][Fe[sub 3]Mo[sub 12]O[sub 30](H[sub x]PO[sub 4])[sub 8]][center dot]16H[sub 2]O (2) (TMA = (CH[sub 3])[sub 4]N[sup +]), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction and water absorption isotherms. Phosphate 1 is prepared in 94% yield from Na[sub 2]MoO[sub 4], Mo, FeCl[sub 3], (NH[sub 4])[sub 2]HPO[sub 4], (TMA)OH, H[sub 3]PO[sub 4], and H[sub 2]O in a mole ratio of 5:1:1:2:7:16:150 at 200[degrees]C for 64 h, while 2 is synthesizedmore » in 62% yield by the reaction of Na[sub 2]MoO[sub 4], Mo, FeCl[sub 3], (TMA)OH, H[sub 3]PO[sub 4] and H[sub 2]O in a mole ratio of 5:1:1:8:18:250 at 200[degrees]C for 3 days. Orange crystals of 1 are rhombohedral. Both structures are based on Fe[Mo[sub 6]O[sub 15](H[sub x]PO[sub 4])[sub 2]] units which are connected via their phosphate groups to additional Fe[sup 3+] ions to give three-dimensional frameworks. Both compounds display structures that can be rationalized on the basis of regions of hydrophobic and hydrophilic interactions. The interconnected voids and channels in the ferric molybdenum phosphate frameworks are filled with a mixture of charged-compensating cations and water of solvation. Reversible water absorption isotherms indicate that both compounds are microporous with internal void volumes of about 15 and 25 vol % for 1 and 2, respectively. 23 refs., 10 figs., 3 tabs.« less
  • Single crystals of (NH{sub 3}(CH{sub 2}){sub 3}NH{sub 3})(H{sub 3}O){sub 2}(UO{sub 2}){sub 3}(MoO{sub 4}){sub 5} (1), C(NH{sub 2}){sub 3}(UO{sub 2})(OH)(MoO{sub 4}) (2), (C{sub 4}H{sub 12}N{sub 2})(UO{sub 2})(MoO{sub 4}){sub 2} (3) and (C{sub 5}H{sub 14}N{sub 2})(UO{sub 2})(MoO{sub 4}){sub 2}{center_dot}H{sub 2}O (4) have been synthesized hydrothermally by using UO{sub 2}(CH{sub 3}COO){sub 2}{center_dot}2H{sub 2}O, (NH{sub 4}){sub 2}Mo{sub 2}O{sub 7}, HF{sub (aq)}, H{sub 2}O, and the respective organic template. The materials have layered structures with anionic uranium molybdate sheets separated by cationic organic templates. Compound 1 has an unprecedented uranium molybdate topology, whereas 2 is structurally related to johannite, Cu[(UO{sub 2}){sub 2}(SO{sub 4}){sub 2}(OH){sub 2}](H{submore » 2}O){sub 8}, and 3 and f4 have layer topologies similar to zippiete, K{sub 2}[UO{sub 2}(MoO{sub 4}){sub 2}]. Thermogravimetric measurements indicate all that four materials, after template loss, form a crystalline mixture of UO{sub 2}MoO{sub 4} and MoO{sub 3}. Crystal data: (NH{sub 3}(CH{sub 2}){sub 3}(H{sub 3}O){sub 2}(UO{sub 2}){sub 3}(MoO{sub 4}){sub 5}, orthorhombic, space group Pbnm (No. 62), with a = 10.465(1) {angstrom}, b = 16.395(1) {angstrom}, c = 20.241(1) {angstrom}, and Z = 4; C(NH{sub 2}){sub 3}(UO{sub 2})(OH)MoO{sub 4}), monoclinic, space group P2{sub 1}/c (No. 14), with a = 15.411(1) {angstrom}, b = 7.086(1) {angstrom}, c = 18.108(1) {angstrom}, {beta} = 113.125(2){degree}, and Z = 4; (C{sub 4}H{sub 12}N{sub 2})(UO{sub 2})(MoO{sub 4}){sub 2}, triclinic, space group P{bar 1} (No. 2), with a = 7.096(1) {angstrom}, b = 8.388(1) {angstrom}, c = 11.634(1) {angstrom}, {alpha} = 97.008(3){degree}, {beta} = 96.454(2){degree}, {gamma} = 110.456(3){degree}, and Z = 2; (C{sub 5}H{sub 14}N{sub 2})(UO{sub 2})(MoO{sub 4}){sub 2}{center_dot}H{sub 2}O, orthorhombic, space group Pbca (No. 61), with a = 12.697(1) {angstrom}, b = 13.247(1) {angstrom}, c = 17.793(1) {angstrom}, and Z = 8.« less