Crystal Structure and Formation of TlPd<sub>3</sub>and its new Hydride TlPd<sub>3</sub>H

Kurtzemann, Nadine; Kohlmann, Holger

doi:10.1002/zaac.201000012

Cited by 21 publications

(25 citation statements)

References 54 publications

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“…[56] Palladium rich intermetallics MPd 3 (M = Mg, In, Tl, Mn) react with hydrogen by intercalating hydrogen in octahedral voids. [87][88][89][90] In situ neutron powder diffraction revealed a detailed picture of the reaction pathway. Hydrogen is incorporated into [Pd 6 ] voids of a ZrAl 3 type structure (fourfold superstructure of the cubic close packing), for higher gas pressures [MPd 5 ] and later [M 2 Pd 4 ] are also occupied for M = Mg. [61] Electronic structure calculations show that this is driven by gaining Pd-H binding energy, however at the same time weakens the cohesion energy between the metal atoms.…”

Section: /Kap1mentioning

confidence: 99%

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Chemical Reactions followed by in situ Neutron Powder Diffraction

Hansen

Kohlmann

2014

Zeitschrift anorg allge chemie

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Abstract. In situ neutron powder diffraction is a very convenient tool for the investigation of chemical reactions, whenever crystalline solids are involved. It may give insight into reaction pathways, thus allowing for strategic synthesis planning, revealing particular intermediate steps and quantifying the reaction kinetics. Although the method is rather straightforward, one is bound to a small number of available neutron sources and the few sufficiently high intensity powder diffractometers there, most of which are briefly described herein. The high penetration depth of thermal neutrons allows for a large range of complex sample environments; however neutron absorption and parasitic scattering have to be carefully considered in the construction of dedicated in situ equipment. Some specific types of sample environment, specially designed for in situ neutron powder diffraction will be discussed such

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Section: /Kap1mentioning

confidence: 99%

“…Palladium rich intermetallics M Pd 3 ( M = Mg, In, Tl, Mn) react with hydrogen by intercalating hydrogen in octahedral voids 87–90 . In situ neutron powder diffraction revealed a detailed picture of the reaction pathway.…”

Section: Examples From Inorganic Chemistrymentioning

confidence: 99%

Chemical Reactions followed by in situ Neutron Powder Diffraction

Hansen

Kohlmann

2014

Zeitschrift anorg allge chemie

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“…[40] For (Sc 3 N)In the transition from the hexagonal binary intermetallic compound to the cubic perovskite indicates a structure determining effect of the nitride ion, as discussed in more detail for the reversible case of related perovskite hydrides. [51] All compounds (R 3 N)In readily react with excess N 2 at elevated temperatures forming the binary rareearth metal nitride RN and In metal. [52] Figure 6.…”

Section: Inverse Perovskite Nitrides With Indium: (R 3 N)inmentioning

confidence: 99%

Metal‐Rich Ternary Perovskite Nitrides

Niewa

2019

Eur J Inorg Chem

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Research interest in inverse perovskite nitrides, since the early beginnings in the 1940s has considerably intensified in recent years. Within the last decades exploration lead to a wide variety of new compounds, compositions and structural arrangements. Electronic properties of the novel materials span from insulating and semiconducting via semimetallic and metallic, depending on element combination. Similarly, magnetic properties qualify for various applications, according to frequently high Curie temperatures and saturation magnetizations, together with development of delicate magnetic structures and often occurring metamagnetic transitions, to give only few examples. This minireview is intended to give an overview on formation of such metal‐rich compounds with focus on chemical systems and crystal chemistry.

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“…TlPd 3 O 4 decomposes to the intermetallic compound TlPd 3 (ZrAl 3 type) and oxygen gas when heated in nitrogen atmosphere to high temperatures. TlPd 3 O 4 is also known to react to β‐TlPd 3 H ( anti ‐perovskite type, Figure ) in hydrogen atmosphere . The close structural relationship between TlPd 3 O 4 and β‐TlPd 3 H might be taken as a hint to a possible topotactic reaction mechanism.…”

Section: Introductionmentioning

confidence: 99%

“…However, the volume effect is huge and half of all atoms from the starting materials are removed in the course of the reaction, making a topotactic reaction rather unlikely. Running the hydrogenation reaction at low chemical potential of hydrogen (7.5 % hydrogen in argon) apparently favors the formation of a metastable hydride α‐TlPd 3 H ≈0.2 with tetragonal ZrAl 3 type structure (hydrogen positions not determined yet) . For both reactions of TlPd 3 O 4 , decomposition in nitrogen atmosphere and the hydride formation in hydrogen atmosphere, the reaction pathway has not been investigated and it is thus unclear whether intermediate phases exist.…”

Section: Introductionmentioning

confidence: 99%

In situ X‐ray Powder Diffraction Study of the Reactions of CrO₂ and TlPd₃O₄ with Hydrogen

Gehlhaar

Keilholz

Kohlmann

2020

Zeitschrift anorg allge chemie

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Hydrogen is an important reducing agent for transition metal oxides, however, details on reaction pathways are often unknown. Therefore, the reduction of CrO2 and TlPd3O4 was investigated by in situ X‐ray powder diffraction and subsequent Rietveld analysis. CrO2 is reduced by hydrogen gas (0.3 MPa) starting at 180 °C according to 2 CrO2 + H2 → 2 CrOOH. The reaction is complete at 250 °C and there are no signs for intermediates or non‐stoichiometry. In nitrogen atmosphere the reaction TlPd3O4 → TlPd3 + 2 O2 occurs without intermediates in one step starting at about 670 °C. Thermal volume expansion is determined to be V(TlPd3O4) = 880.7(1) 106 pm3 + 1.64(7) 104 T pm3/K + 10.7(9) T2 pm3/K2 and V(TlPd3) = 258.6(1) 106 pm3 + 8.5(7) 103 T pm3/K + 2.6(7) T2 pm3/K2 for 25 °C ≤ T ≤ 730 °C. The formation of β‐TlPd3H from TlPd3O4 in 0.3 MPa hydrogen gas at 75 °C occurs very fast. Unit cell parameters indicate the occurrence of a metastable α‐TlPd3H≈0.2 with a hydrogen‐filled ZrAl3 type. Cubic anti‐perovskite type β‐TlPd3H reacts in air to TlPd3 with a possible hydrogen deficient intermediate β‐TlPd3H1–x and hints for remaining hydrogen in the tetragonal ZrAl3 type intermetallic compound. In situ methods thus give a deeper insight in the TlPd3‐O2‐H2 system with the identification of possible candidates for interesting intermediate phases and more detailed information on thermal stabilities.

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Crystal Structure and Formation of TlPd₃and its new Hydride TlPd₃H

Cited by 21 publications

References 54 publications

Chemical Reactions followed by in situ Neutron Powder Diffraction

Chemical Reactions followed by in situ Neutron Powder Diffraction

Metal‐Rich Ternary Perovskite Nitrides

In situ X‐ray Powder Diffraction Study of the Reactions of CrO₂ and TlPd₃O₄ with Hydrogen

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Crystal Structure and Formation of TlPd3and its new Hydride TlPd3H

Cited by 21 publications

References 54 publications

Chemical Reactions followed by in situ Neutron Powder Diffraction

Chemical Reactions followed by in situ Neutron Powder Diffraction

Metal‐Rich Ternary Perovskite Nitrides

In situ X‐ray Powder Diffraction Study of the Reactions of CrO2 and TlPd3O4 with Hydrogen

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Crystal Structure and Formation of TlPd₃and its new Hydride TlPd₃H

In situ X‐ray Powder Diffraction Study of the Reactions of CrO₂ and TlPd₃O₄ with Hydrogen