I11-High Resolution Powder Diffraction
|
Abstract: Electronic phase separation into charge-ordered (CO) and charge-averaged (CA) phases in
Ca
Fe
3
−
x
M
x
O
5
samples for dopants
M
=
Mn
and Co has been investigated using powder neutron and x-ray diffraction, magnetization, and Mössbauer spectroscopy measurements. Electronic phase separation is observed in lightly doped
Ca
Fe
3
O
5
samples, where
4
–
10
%
Ca is replaced by Mn, Fe, or Co, and the CA ground state is stabilized at higher doping levels. The CO and CA phases are found to emerge below a common magnetic ordering temperature at
300
–
320
K
providing strong evidence for a lattice strain-driven mechanism that couples their magnetic transitions.
|
Feb 2021
|
|
B22-Multimode InfraRed imaging And Microspectroscopy
|
Xue
Han
,
Wanpeng
Lu
,
Yinlin
Chen
,
Ivan
Da Silva
,
Jiangnan
Li
,
Longfei
Lin
,
Weiyao
Li
,
Alena M.
Sheveleva
,
Harry G. W.
Godfrey
,
Zhenzhong
Lu
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Yongqiang
Cheng
,
Luke L.
Daemen
,
Laura J.
Mccormick Mcpherson
,
Simon J.
Teat
,
Mark D.
Frogley
,
Svemir
Rudic
,
Pascal
Manuel
,
Anibal J.
Ramirez-cuesta
,
Sihai
Yang
,
Martin
Schroeder
Diamond Proposal Number(s):
[23782]
Abstract: Ammonia (NH3) is a promising energy resource owing to its high hydrogen density. However, its widespread application is restricted by the lack of efficient and corrosion-resistant storage materials. Here, we report high NH3 adsorption in a series of robust metal–organic framework (MOF) materials, MFM-300(M) (M = Fe, V, Cr, In). MFM-300(M) (M = Fe, VIII, Cr) show fully reversible capacity for >20 cycles, reaching capacities of 16.1, 15.6, and 14.0 mmol g–1, respectively, at 273 K and 1 bar. Under the same conditions, MFM-300(VIV) exhibits the highest uptake among this series of MOFs of 17.3 mmol g–1. In situ neutron powder diffraction, single-crystal X-ray diffraction, and electron paramagnetic resonance spectroscopy confirm that the redox-active V center enables host–guest charge transfer, with VIV being reduced to VIII and NH3 being oxidized to hydrazine (N2H4). A combination of in situ inelastic neutron scattering and DFT modeling has revealed the binding dynamics of adsorbed NH3 within these MOFs to afford a comprehensive insight into the application of MOF materials to the adsorption and conversion of NH3.
|
Feb 2021
|
|
I11-High Resolution Powder Diffraction
|
Tatchamapan
Yoskamtorn
,
Pu
Zhao
,
Xin-ping
Wu
,
Kirsty
Purchase
,
Fabio
Orlandi
,
Pascal
Manuel
,
James
Taylor
,
Yiyang
Li
,
Sarah
Day
,
Lin
Ye
,
Chiu C.
Tang
,
Yufei
Zhao
,
S. C. Edman
Tsang
Abstract: Understanding structural responses of metal–organic frameworks (MOFs) to external stimuli such as the inclusion of guest molecules and temperature/pressure has gained increasing attention in many applications, for example, manipulation and manifesto smart materials for gas storage, energy storage, controlled drug delivery, tunable mechanical properties, and molecular sensing, to name but a few. Herein, neutron and synchrotron diffractions along with Rietveld refinement and density functional theory calculations have been used to elucidate the responsive adsorption behaviors of defect-rich Zr-based MOFs upon the progressive incorporation of ammonia (NH3) and variable temperature. UiO-67 and UiO-bpydc containing biphenyl dicarboxylate and bipyridine dicarboxylate linkers, respectively, were selected, and the results establish the paramount influence of the functional linkers on their NH3 affinity, which leads to stimulus-tailoring properties such as gate-controlled porosity by dynamic linker flipping, disorder, and structural rigidity. Despite their structural similarities, we show for the first time the dramatic alteration of NH3 adsorption profiles when the phenyl groups are replaced by the bipyridine in the organic linker. These molecular controls stem from controlling the degree of H-bonding networks/distortions between the bipyridine scaffold and the adsorbed NH3 without significant change in pore volume and unit cell parameters. Temperature-dependent neutron diffraction also reveals the NH3-induced rotational motions of the organic linkers. We also demonstrate that the degree of structural flexibility of the functional linkers can critically be affected by the type and quantity of the small guest molecules. This strikes a delicate control in material properties at the molecular level.
|
Feb 2021
|
|
I11-High Resolution Powder Diffraction
|
Henrik
Jacobsen
,
Hai L.
Feng
,
Andrew J.
Princep
,
Marein C.
Rahn
,
Yanfeng
Guo
,
Jie
Chen
,
Yoshitaka
Matsushita
,
Yoshihiro
Tsujimoto
,
Masahiro
Nagao
,
Dmitry
Khalyavin
,
Pascal
Manuel
,
Claire A.
Murray
,
Christian
Donnerer
,
James G.
Vale
,
Marco
Moretti Sala
,
Kazunari
Yamaura
,
Andrew T.
Boothroyd
Diamond Proposal Number(s):
[9839]
Abstract: We report on the structural, magnetic, and electronic properties of two new double-perovskites synthesized under high pressure,
Pb
2
CaOsO
6
and
Pb
2
ZnOsO
6
. Upon cooling below 80 K,
Pb
2
CaOsO
6
simultaneously undergoes a metal-to-insulator transition and develops antiferromagnetic order.
Pb
2
ZnOsO
6
, on the other hand, remains a paramagnetic metal down to 2 K. The key difference between the two compounds lies in their crystal structures. The Os atoms in
Pb
2
ZnOsO
6
are arranged on an approximately face-centered cubic lattice with strong antiferromagnetic nearest-neighbor exchange couplings. The geometrical frustration inherent to this lattice prevents magnetic order from forming down to the lowest temperatures. In contrast, the unit cell of
Pb
2
CaOsO
6
is heavily distorted up to at least 500 K including antiferroelectriclike displacements of the Pb and O atoms despite metallic conductivity above 80 K. This distortion relieves the magnetic frustration, facilitating magnetic order which, in turn, drives the metal-insulator transition. Our results suggest that the phase transition in
Pb
2
CaOsO
6
is spin driven and could be a rare example of a Slater transition.
|
Dec 2020
|
|
I16-Materials and Magnetism
|
C. D.
Dashwood
,
L. S. I.
Veiga
,
Q.
Faure
,
J. G.
Vale
,
D. G.
Porter
,
S. P.
Collins
,
P.
Manuel
,
D. D.
Khalyavin
,
F.
Orlandi
,
R. S.
Perry
,
R. D.
Johnson
,
D. F.
Mcmorrow
Diamond Proposal Number(s):
[23580]
Abstract: We show how complex modulated order can spontaneously emerge when magnetic interactions compete in a metal with polar lattice distortions. Combining neutron and resonant x-ray scattering with symmetry analysis, we reveal that the spin reorientation in
Ca
3
Ru
2
O
7
is mediated by a magnetic cycloid whose eccentricity evolves smoothly but rapidly with temperature. We find the cycloid to be highly sensitive to magnetic fields, which appear to continuously generate higher harmonic modulations. Our results provide a unified picture of the rich magnetic phases of this correlated, multiband polar metal.
|
Nov 2020
|
|
I11-High Resolution Powder Diffraction
|
Diamond Proposal Number(s):
[13284, 18786]
Abstract: Sr2CrO2Cr2As2 and Ba2CrO2Cr2As2 with Cr2+ ions in CrO2 sheets and in CrAs layers crystallize with the Sr2Mn3Sb2O2 structure (space group I4/mmm, Z = 2) and lattice parameters a = 4.00800(2) Å, c = 18.8214(1) Å (Sr2CrO2Cr2As2) and a = 4.05506(2) Å, c = 20.5637(1) Å (Ba2CrO2Cr2As2) at room temperature. Powder neutron diffraction reveals checkerboard-type antiferromagnetic ordering of the Cr2+ ions in the arsenide layers below TN1_Sr, of 600(10) K (Sr2CrO2Cr2As2) and TN1_Ba 465(5) K (Ba2CrO2Cr2As2) with the moments initially directed perpendicular to the layers in both compounds. Checkerboard-type antiferromagnetic ordering of the Cr2+ ions in the oxide layer below 230(5) K for Ba2CrO2Cr2As2 occurs with these moments also perpendicular to the layers, consistent with the orientation preferences of d4 moments in the two layers. In contrast, below 330(5) K in Sr2CrO2Cr2As2, the oxide layer Cr2+ moments are initially oriented in the CrO2 plane; but on further cooling, these moments rotate to become perpendicular to the CrO2 planes, while the moments in the arsenide layers rotate by 90° with the moments on the two sublattices remaining orthogonal throughout [behavior recently reported independently by Liu et al. [Liu et al. Phys. Rev. B 2018, 98, 134416]]. In Sr2CrO2Cr2As2, electron diffraction and high resolution powder X-ray diffraction data show no evidence for a structural distortion that would allow the two Cr2+ sublattices to couple, but high resolution neutron powder diffraction data suggest a small incommensurability between the magnetic structure and the crystal structure, which may account for the coupling of the two sublattices and the observed spin reorientation. The saturation values of the Cr2+ moments in the CrO2 layers (3.34(1) μB (for Sr2CrO2Cr2As2) and 3.30(1) μB (for Ba2CrO2Cr2As2)) are larger than those in the CrAs layers (2.68(1) μB for Sr2CrO2Cr2As2 and 2.298(8) μB for Ba2CrO2Cr2As2) reflecting greater covalency in the arsenide layers.
|
Oct 2020
|
|
I11-High Resolution Powder Diffraction
I19-Small Molecule Single Crystal Diffraction
|
Stephen P.
Argent
,
Ivan
Da Silva
,
Alex
Greenaway
,
Mathew
Savage
,
Jack
Humby
,
Andrew J.
Davies
,
Harriott
Nowell
,
William
Lewis
,
Pascal
Manuel
,
Chiu C.
Tang
,
Alexander J.
Blake
,
Michael W.
George
,
Alexander V.
Markevich
,
Elena
Besley
,
Sihai
Yang
,
Neil R.
Champness
,
Martin
Schroeder
Diamond Proposal Number(s):
[861, 11622, 15833, 9443]
Open Access
Abstract: Designing porous materials which can selectively adsorb CO2 or CH4 is an important environmental and industrial goal which requires an understanding of the host–guest interactions involved at the atomic scale. Metal–organic polyhedra (MOPs) showing permanent porosity upon desolvation are rarely observed. We report a family of MOPs (Cu-1a, Cu-1b, Cu-2), which derive their permanent porosity from cavities between packed cages rather than from within the polyhedra. Thus, for Cu-1a, the void fraction outside the cages totals 56% with only 2% within. The relative stabilities of these MOP structures are rationalized by considering their weak nondirectional packing interactions using Hirshfeld surface analyses. The exceptional stability of Cu-1a enables a detailed structural investigation into the adsorption of CO2 and CH4 using in situ X-ray and neutron diffraction, coupled with DFT calculations. The primary binding sites for adsorbed CO2 and CH4 in Cu-1a are found to be the open metal sites and pockets defined by the faces of phenyl rings. More importantly, the structural analysis of a hydrated sample of Cu-1a reveals a strong hydrogen bond between the adsorbed CO2 molecule and the Cu(II)-bound water molecule, shedding light on previous empirical and theoretical observations that partial hydration of metal−organic framework (MOF) materials containing open metal sites increases their uptake of CO2. The results of the crystallographic study on MOP–gas binding have been rationalized using DFT calculations, yielding individual binding energies for the various pore environments of Cu-1a.
|
Oct 2020
|
|
B22-Multimode InfraRed imaging And Microspectroscopy
|
Thien D.
Duong
,
Sergey A.
Sapchenko
,
Ivan
Da Silva
,
Harry G. W.
Godfrey
,
Yongqiang
Cheng
,
Luke L.
Daemen
,
Pascal
Manuel
,
Mark D.
Frogley
,
Gianfelice
Cinque
,
Anibal J.
Ramirez-cuesta
,
Sihai
Yang
,
Martin
Schroeder
Diamond Proposal Number(s):
[14938]
Open Access
Abstract: Metal–organic frameworks (MOFs) functionalised with amine, amide and hydroxyl groups show great promise for CO2 binding due to their ability to form hydrogen bonds to CO2. Herein we report the adsorption and selectivity of CO2 in four iso-reticular MOFs adopting the NbO topology. Functionalisation of the parent MOF, MFM-102, with –NO2, –NH2 and alkyl groups leads to an enhancement of CO2 adsorption of up to 36% for the NO2-decorated MOF and with raised selectivity. MFM-102-NO2 shows the highest adsorption capacity for CO2 (184 cm3 g−1 at 273 K and 1.0 bar) within this series, comparable to the best-behaving iso-reticular MOFs. At 298 K and 1.0 bar, MFM-102-NO2 shows a CO2/CH4 selectivity of 5.0. In situ inelastic neutron scattering and synchrotron FT-IR micro-spectroscopy were employed to elucidate the host–guest interaction dynamics within CO2-loaded MFM-102-NO2. Neutron powder diffraction enabled the direct observation of the preferred binding domains in MFM-102-NO2, and, to the best of our knowledge, we report the first example of CO2 binding to a –NO2 group in a porous MOF. Synergistic effects between the –NO2 group and the open metal sites lead to optimal binding of CO2 molecules within MFM-102-NO2 via hydrogen bonding to C–H groups.
|
May 2020
|
|
I11-High Resolution Powder Diffraction
|
Yuchao
Chai
,
Xue
Han
,
Weiyao
Li
,
Shanshan
Liu
,
Sikai
Yao
,
Chong
Wang
,
Wei
Shi
,
Ivan
Da Silva
,
Pascal
Manuel
,
Yongqiang
Cheng
,
Luke D.
Daemen
,
Anibal J.
Ramirez-cuesta
,
Chiu C.
Tang
,
Ling
Jiang
,
Sihai
Yang
,
Naijia
Guan
,
Landong
Li
Diamond Proposal Number(s):
[23483]
Open Access
Abstract: The efficient removal of alkyne impurities for the production of polymer-grade lower olefins remains an important and challenging goal for many industries. We report a strategy to control the pore interior of faujasite (FAU) zeolites by the confinement of isolated open nickel(II) sites in their six-membered rings. Under ambient conditions, Ni@FAU showed remarkable adsorption of alkynes and efficient separations of acetylene/ethylene, propyne/propylene, and butyne/1,3-butadiene mixtures, with unprecedented dynamic separation selectivities of 100, 92, and 83, respectively. In situ neutron diffraction and inelastic neutron scattering revealed that confined nickel(II) sites enabled chemoselective and reversible binding to acetylene through the formation of metastable [Ni(II)(C2H2)3] complexes. Control of the chemistry of pore interiors of easily scalable zeolites has unlocked their potential in challenging industrial separations.
|
May 2020
|
|
I11-High Resolution Powder Diffraction
|
Diamond Proposal Number(s):
[13284, 18786]
Open Access
Abstract: Mixed-valent transition metal compounds display complex structural, electronic and magnetic properties which can often be exquisitely tuned. Here the charge-ordered state of stoichiometric CaFe3O5 is probed using neutron powder diffraction, Monte Carlo simulation and symmetry analysis. Magnetic ordering is dominated by the formation of ferromagnetic Fe3+–Fe2+–Fe3+ trimers which are evident above the magnetic ordering transition. Between TN = 289 K and 281 K an incommensurate magnetically ordered phase develops due to magnetic frustration, but a spin Jahn-Teller distortion lifts the frustration and enables the magnetic ordering to lock in to a charge-ordered commensurate state at lower temperatures. Stoichiometric CaFe3O5 exhibits single phase behaviour throughout and avoids the phase separation into two distinct crystallographic phases with different magnetic structures and Fe valence distributions reported recently, which likely occurs due to partial Fe2+ for Ca2+ substitution. This underlines the sensitivity of the magnetism and chemistry of these mixed-valent systems to composition.
|
Dec 2019
|
|
