Privileged metal cluster complexes
Gas-phase reactions of rhodium and platinum clusters with common ligand molecules in forming metal complexes, showing privileged cluster complexes with adaptive electron delocalization.
Chemistry↗
SEARCH · Engineering Papers
Results for “rhodium”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Xenon–metal pair formation in UO 2 investigated using DFT + U
A recent experimental study on a spent uranium dioxide (UO 2 ) fuel sample from Belgium Reactor 3 identified a unique pair structure formed by the noble metal phase (NMP) and fission gas [xenon (Xe)] precipitate. However, the fundamental mechanism behind this structure remains unclear. The present study aims to provide an understanding of the interaction between five different metal precipitates [molybdenum (Mo), ruthenium (Ru), palladium (Pd), technetium (Tc), and rhodium (Rh)] and the Xe fission gas atoms in UO 2 , by using density functional theory (DFT) in combination with the Hubbard U correction to compute the formation energies involved. All DFT + U calculations were performed with occupation matrix control to ensure antiferromagnetic ordering of UO 2 . The calculated formation and binding energies of the Xe and solid fission products in the NMP reveal that these metal precipitates form stable pair structures with Xe. Notably, the formation energy of Xe–metal pairs is lower than that of the isolated single defects in all instances, with Pd and Mo showing the most favorable binding energy, likely accounting for the observed pair structure formation.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
Charge-ordered state satisfying the Anderson condition in LiRh 2 O 4 arising from local dimer order
Here we report on the charge-ordered structure of LiRh 2 O 4 arising below the metal-insulator transition at 170 K. Structural studies using synchrotron x rays have revealed that the charge-ordered states of Rh 3+ and Rh 4+ with dimerization are realized in the low-temperature phase below 170 K. Although the low-temperature ground state resembles that of CuIr 2 S 4 , a charge-ordering pattern satisfying the Anderson condition is realized in LiRh 2 O 4 . Based on structural information such as the short-range order of dimers appearing above the transition temperature and the weakening of the correlation between rhodium one-dimensional chains appearing in the crystal structure, we argue that the Coulomb interaction plays an important role in determining the charge-ordering patterns.
36 MATERIALS SCIENCE↗
Structure transition and zigzag magnetic order in Ir/Rh-substituted honeycomb lattice α - RuCl 3
Here, we report magnetization and neutron diffraction studies on crystal and magnetic structures of Ir- and Rh-substituted honeycomb lattice α-RuCl 3 . The iridium or rhodium atoms are distributed at the Ru site with little structural modification. Both systems undergo a room-temperature monoclinic C2/m to low-temperature trigonal $R\bar{3}$ phase transformation with a large recoverable hysteresis. At low temperature, a zigzag spin order is observed with the same characteristic wave vector (0,0.5,1) as in the parent α-RuCl 3 . Detailed magnetic structure refinement reveals an ordered moment of 0.32(5)µB/Ru and an upper boundary of canting angle of 15(4)º away from the basal plane at 5 K for the 10% Ir-substituted α-RuCl 3 , which is different from the 0.45–0.73 µB/Ru and 32°–48° canting angle reported in the parent compound α-RuCl 3 . The observation of unchanged RuCl 6 local octahedral environment, reduced ordered magnetic moment size and canting angle compared to previously reported highlights the potential to study quantum spin-liquid behavior through nonmagnetic ion doping.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
First-principles design of a single-atom–alloy propane dehydrogenation catalyst
The complexity of heterogeneous catalysts means that a priori design of new catalytic materials is difficult, but the well-defined nature of single-atom–alloy catalysts has made it feasible to perform unambiguous theoretical modeling and precise surface science experiments. Herein we report the theory-led discovery of a rhodium-copper (RhCu) single-atom–alloy catalyst for propane dehydrogenation to propene. Although Rh is not generally considered for alkane dehydrogenation, first-principles calculations revealed that Rh atoms disperse in Cu and exhibit low carbon-hydrogen bond activation barriers. Surface science experiments confirmed these predictions, and together these results informed the design of a highly active, selective, and coke-resistant RhCu nanoparticle catalyst that enables low-temperature nonoxidative propane dehydrogenation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Tracking C–H activation with orbital resolution
Transition metal reactivity toward carbon–hydrogen (C–H) bonds hinges on the interplay of electron donation and withdrawal at the metal center. Manipulating this reactivity in a controlled way is difficult because the hypothesized metal-alkane charge-transfer interactions are challenging to access experimentally. Using time-resolved x-ray spectroscopy, we track the charge-transfer interactions during C–H activation of octane by a cyclopentadienyl rhodium carbonyl complex. Changes in oxidation state as well as valence-orbital energies and character emerge in the data on a femtosecond to nanosecond timescale. The x-ray spectroscopic signatures reflect how alkane-to-metal donation determines metal-alkane complex stability and how metal-to-alkane back-donation facilitates C–H bond cleavage by oxidative addition. Furthermore, the ability to dissect charge-transfer interactions on an orbital level provides opportunities for manipulating C–H reactivity at transition metals.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Materials Data on Na3Rh(NO2)6 by Materials Project
(Na(NO2)2)3Rh crystallizes in the trigonal R-3m space group. The structure is three-dimensional and consists of three rhodium molecules and one Na(NO2)2 framework. In the Na(NO2)2 framework, there are two inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded to six O2- atoms to form a mixture of corner and face-sharing NaO6 octahedra. There are three shorter (2.36 Å) and three longer (2.41 Å) Na–O bond lengths. In the second Na1+ site, Na1+ is bonded to twelve O2- atoms to form a mixture of corner and face-sharing NaO12 cuboctahedra. The corner-sharing octahedral tilt angles are 45°. There are six shorter (2.66 Å) and six longer (2.95 Å) Na–O bond lengths. N3+ is bonded in a bent 120 degrees geometry to two O2- atoms. There is one shorter (1.24 Å) and one longer (1.25 Å) N–O bond length. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a 3-coordinate geometry to two Na1+ and one N3+ atom. In the second O2- site, O2- is bonded in a 2-coordinate geometry to two Na1+ and one N3+ atom.
36 MATERIALS SCIENCE↗
Materials Data on K3Rh(NO2)6 by Materials Project
K(K(NO2)3)2Rh crystallizes in the cubic Fm-3m space group. The structure is three-dimensional and consists of four potassium molecules, four rhodium molecules, and one K(NO2)3 framework. In the K(NO2)3 framework, K1+ is bonded in a distorted q4 geometry to twelve equivalent O2- atoms. All K–O bond lengths are 2.68 Å. N3+ is bonded in a rectangular see-saw-like geometry to four equivalent O2- atoms. All N–O bond lengths are 2.12 Å. O2- is bonded to two equivalent K1+, two equivalent N3+, and one O2- atom to form a mixture of distorted edge and corner-sharing OK2N2O square pyramids. The O–O bond length is 1.34 Å.
36 MATERIALS SCIENCE↗
Materials Data on P2RhClF6 by Materials Project
RhCl(PF3)2 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of four dichlororhodium;rhodium molecules and sixteen phosphorus trifluoride molecules.
36 MATERIALS SCIENCE↗
Materials Data on Si2Bi14RhI12 by Materials Project
Rh(SiBi7I6)2 crystallizes in the tetragonal P4/mcc space group. The structure is two-dimensional and consists of two rhodium molecules and two SiBi7I6 sheets oriented in the (0, 0, 1) direction. In each SiBi7I6 sheet, Si4- is bonded in a 4-coordinate geometry to four equivalent Bi+1.21+ atoms. All Si–Bi bond lengths are 2.90 Å. There are three inequivalent Bi+1.21+ sites. In the first Bi+1.21+ site, Bi+1.21+ is bonded in a distorted square co-planar geometry to four I1- atoms. There are a spread of Bi–I bond distances ranging from 3.17–3.29 Å. In the second Bi+1.21+ site, Bi+1.21+ is bonded in a distorted water-like geometry to one Si4- and one I1- atom. The Bi–I bond length is 3.73 Å. In the third Bi+1.21+ site, Bi+1.21+ is bonded in a distorted square co-planar geometry to four equivalent I1- atoms. All Bi–I bond lengths are 3.24 Å. There are two inequivalent I1- sites. In the first I1- site, I1- is bonded in a 2-coordinate geometry to two equivalent Bi+1.21+ atoms. In the second I1- site, I1- is bonded in a 3-coordinate geometry to three Bi+1.21+ atoms.
36 MATERIALS SCIENCE↗
Materials Data on Ga2RhC4Cl7O4 by Materials Project
RhGa2Cl7(CO)4 crystallizes in the triclinic P-1 space group. The structure is zero-dimensional and consists of eight formaldehyde molecules, two rhodium molecules, and two Ga2Cl7 clusters. In each Ga2Cl7 cluster, there are two inequivalent Ga3+ sites. In the first Ga3+ site, Ga3+ is bonded to four Cl1- atoms to form corner-sharing GaCl4 tetrahedra. There are a spread of Ga–Cl bond distances ranging from 2.16–2.38 Å. In the second Ga3+ site, Ga3+ is bonded to four Cl1- atoms to form corner-sharing GaCl4 tetrahedra. There are a spread of Ga–Cl bond distances ranging from 2.17–2.32 Å. There are seven inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+ atom. In the second Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+ atom. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+ atom. In the fourth Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+ atom. In the fifth Cl1- site, Cl1- is bonded in a bent 120 degrees geometry to two Ga3+ atoms. In the sixth Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+ atom. In the seventh Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+ atom.
36 MATERIALS SCIENCE↗
Materials Data on Al2RhC4Cl7O4 by Materials Project
RhAl2Cl7(CO)4 crystallizes in the triclinic P-1 space group. The structure is zero-dimensional and consists of eight formaldehyde molecules, two rhodium molecules, and two Al2Cl7 clusters. In each Al2Cl7 cluster, there are two inequivalent Al3+ sites. In the first Al3+ site, Al3+ is bonded to four Cl1- atoms to form corner-sharing AlCl4 tetrahedra. There are a spread of Al–Cl bond distances ranging from 2.12–2.30 Å. In the second Al3+ site, Al3+ is bonded to four Cl1- atoms to form corner-sharing AlCl4 tetrahedra. There are a spread of Al–Cl bond distances ranging from 2.13–2.26 Å. There are seven inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to one Al3+ atom. In the second Cl1- site, Cl1- is bonded in a bent 120 degrees geometry to two Al3+ atoms. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one Al3+ atom. In the fourth Cl1- site, Cl1- is bonded in a single-bond geometry to one Al3+ atom. In the fifth Cl1- site, Cl1- is bonded in a single-bond geometry to one Al3+ atom. In the sixth Cl1- site, Cl1- is bonded in a single-bond geometry to one Al3+ atom. In the seventh Cl1- site, Cl1- is bonded in a single-bond geometry to one Al3+ atom.
36 MATERIALS SCIENCE↗
Materials Data on H3Ru3Rh(CO)12 by Materials Project
Rh(RuH(CO)3)3(CO)3 crystallizes in the triclinic P-1 space group. The structure is zero-dimensional and consists of six formaldehyde molecules, two rhodium molecules, and two RuH(CO)3 clusters. In each RuH(CO)3 cluster, there are three inequivalent Ru+3.33+ sites. In the first Ru+3.33+ site, Ru+3.33+ is bonded in a 5-coordinate geometry to three C+0.67+ and two H1+ atoms. There is one shorter (1.90 Å) and two longer (1.91 Å) Ru–C bond length. There is one shorter (1.79 Å) and one longer (1.83 Å) Ru–H bond length. In the second Ru+3.33+ site, Ru+3.33+ is bonded in a 5-coordinate geometry to three C+0.67+ and two H1+ atoms. All Ru–C bond lengths are 1.91 Å. Both Ru–H bond lengths are 1.80 Å. In the third Ru+3.33+ site, Ru+3.33+ is bonded in a 5-coordinate geometry to three C+0.67+ and two H1+ atoms. All Ru–C bond lengths are 1.91 Å. There is one shorter (1.79 Å) and one longer (1.80 Å) Ru–H bond length. There are nine inequivalent C+0.67+ sites. In the first C+0.67+ site, C+0.67+ is bonded in a single-bond geometry to one Ru+3.33+ and one O2- atom. The C–O bond length is 1.16 Å. In the second C+0.67+ site, C+0.67+ is bonded in a single-bond geometry to one Ru+3.33+ and one O2- atom. The C–O bond length is 1.16 Å. In the third C+0.67+ site, C+0.67+ is bonded in a single-bond geometry to one Ru+3.33+ and one O2- atom. The C–O bond length is 1.16 Å. In the fourth C+0.67+ site, C+0.67+ is bonded in a single-bond geometry to one Ru+3.33+ and one O2- atom. The C–O bond length is 1.16 Å. In the fifth C+0.67+ site, C+0.67+ is bonded in a single-bond geometry to one Ru+3.33+ and one O2- atom. The C–O bond length is 1.16 Å. In the sixth C+0.67+ site, C+0.67+ is bonded in a single-bond geometry to one Ru+3.33+ and one O2- atom. The C–O bond length is 1.16 Å. In the seventh C+0.67+ site, C+0.67+ is bonded in a single-bond geometry to one Ru+3.33+ and one O2- atom. The C–O bond length is 1.16 Å. In the eighth C+0.67+ site, C+0.67+ is bonded in a single-bond geometry to one Ru+3.33+ and one O2- atom. The C–O bond length is 1.16 Å. In the ninth C+0.67+ site, C+0.67+ is bonded in a single-bond geometry to one Ru+3.33+ and one O2- atom. The C–O bond length is 1.16 Å. There are three inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a water-like geometry to two Ru+3.33+ atoms. In the second H1+ site, H1+ is bonded in a water-like geometry to two Ru+3.33+ atoms. In the third H1+ site, H1+ is bonded in a water-like geometry to two Ru+3.33+ atoms. There are nine inequivalent O2- sites. In the first O2- site, O2- is bonded in a single-bond geometry to one C+0.67+ atom. In the second O2- site, O2- is bonded in a single-bond geometry to one C+0.67+ atom. In the third O2- site, O2- is bonded in a single-bond geometry to one C+0.67+ atom. In the fourth O2- site, O2- is bonded in a single-bond geometry to one C+0.67+ atom. In the fifth O2- site, O2- is bonded in a single-bond geometry to one C+0.67+ atom. In the sixth O2- site, O2- is bonded in a single-bond geometry to one C+0.67+ atom. In the seventh O2- site, O2- is bonded in a single-bond geometry to one C+0.67+ atom. In the eighth O2- site, O2- is bonded in a single-bond geometry to one C+0.67+ atom. In the ninth O2- site, O2- is bonded in a single-bond geometry to one C+0.67+ atom.
36 MATERIALS SCIENCE↗
Materials Data on Li3Rh(N3O8)2 by Materials Project
RhLi3(N3O8)2 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of two rhodium molecules and two Li3(N3O8)2 clusters. In each Li3(N3O8)2 cluster, there are two inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded in a 3-coordinate geometry to three O2- atoms. There are a spread of Li–O bond distances ranging from 1.94–2.03 Å. In the second Li1+ site, Li1+ is bonded in an octahedral geometry to six O2- atoms. All Li–O bond lengths are 2.05 Å. There are three inequivalent N+4.33+ sites. In the first N+4.33+ site, N+4.33+ is bonded in a bent 120 degrees geometry to two O2- atoms. There is one shorter (1.23 Å) and one longer (1.27 Å) N–O bond length. In the second N+4.33+ site, N+4.33+ is bonded in a bent 120 degrees geometry to two O2- atoms. There is one shorter (1.23 Å) and one longer (1.24 Å) N–O bond length. In the third N+4.33+ site, N+4.33+ is bonded in a bent 120 degrees geometry to two O2- atoms. There is one shorter (1.23 Å) and one longer (1.25 Å) N–O bond length. There are eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 120 degrees geometry to one Li1+ and one N+4.33+ atom. In the second O2- site, O2- is bonded in a bent 120 degrees geometry to one Li1+ and one N+4.33+ atom. In the third O2- site, O2- is bonded in a trigonal planar geometry to two Li1+ and one N+4.33+ atom. In the fourth O2- site, O2- is bonded in a distorted single-bond geometry to one N+4.33+ atom. In the fifth O2- site, O2- is bonded in a single-bond geometry to one Li1+ atom. In the sixth O2- site, O2- is bonded in a single-bond geometry to one N+4.33+ atom. In the seventh O2- site, O2- is bonded in a single-bond geometry to one N+4.33+ atom. In the eighth O2- site, O2- is bonded in a single-bond geometry to one Li1+ atom.
36 MATERIALS SCIENCE↗
Materials Data on HRuRh(CO)6 by Materials Project
RhRu2RhH2(CO)12 crystallizes in the triclinic P-1 space group. The structure is zero-dimensional and consists of twenty-four formaldehyde molecules, two rhodium molecules, and two Ru2RhH2 clusters. In each Ru2RhH2 cluster, there are two inequivalent Ru2+ sites. In the first Ru2+ site, Ru2+ is bonded in an L-shaped geometry to two H1+ atoms. There is one shorter (1.78 Å) and one longer (1.79 Å) Ru–H bond length. In the second Ru2+ site, Ru2+ is bonded in a distorted single-bond geometry to one H1+ atom. The Ru–H bond length is 1.83 Å. Rh3+ is bonded in a distorted single-bond geometry to one H1+ atom. The Rh–H bond length is 1.78 Å. There are two inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a water-like geometry to one Ru2+ and one Rh3+ atom. In the second H1+ site, H1+ is bonded in a bent 120 degrees geometry to two Ru2+ atoms.
36 MATERIALS SCIENCE↗
Materials Data on NaRh(N2O3)4 by Materials Project
Na(NO2)6RhN2 is Heusler structured and crystallizes in the cubic Fm-3 space group. The structure is zero-dimensional and consists of eight ammonia molecules, four rhodium molecules, and four Na(NO2)6 clusters. In each Na(NO2)6 cluster, Na1+ is bonded in a cuboctahedral geometry to twelve equivalent O2- atoms. All Na–O bond lengths are 2.89 Å. N+2.50+ is bonded in a bent 120 degrees geometry to two equivalent O2- atoms. Both N–O bond lengths are 1.23 Å. O2- is bonded in a single-bond geometry to one Na1+ and one N+2.50+ atom.
36 MATERIALS SCIENCE↗
Materials Data on NaH8Rh(N2O3)4 by Materials Project
Na(NO2)6Rh(NH4)2 is Heusler structured and crystallizes in the cubic Fm-3 space group. The structure is zero-dimensional and consists of eight ammonium molecules, four rhodium molecules, and four Na(NO2)6 clusters. In each Na(NO2)6 cluster, Na1+ is bonded in a cuboctahedral geometry to twelve equivalent O2- atoms. All Na–O bond lengths are 2.92 Å. N+1.50+ is bonded in a bent 120 degrees geometry to two equivalent O2- atoms. Both N–O bond lengths are 1.25 Å. O2- is bonded in a single-bond geometry to one Na1+ and one N+1.50+ atom.
36 MATERIALS SCIENCE↗
Materials Data on NaRh(N2O3)4 by Materials Project
Na(NO2)6RhN2 is Heusler structured and crystallizes in the monoclinic Cm space group. The structure is zero-dimensional and consists of four ammonia molecules, two rhodium molecules, and two Na(NO2)6 clusters. In each Na(NO2)6 cluster, Na1+ is bonded in a cuboctahedral geometry to twelve O2- atoms. There are a spread of Na–O bond distances ranging from 2.88–2.93 Å. There are five inequivalent N+2.50+ sites. In the first N+2.50+ site, N+2.50+ is bonded in a bent 120 degrees geometry to two O2- atoms. Both N–O bond lengths are 1.23 Å. In the second N+2.50+ site, N+2.50+ is bonded in a bent 120 degrees geometry to two equivalent O2- atoms. Both N–O bond lengths are 1.23 Å. In the third N+2.50+ site, N+2.50+ is bonded in a bent 120 degrees geometry to two O2- atoms. Both N–O bond lengths are 1.23 Å. In the fourth N+2.50+ site, N+2.50+ is bonded in a bent 120 degrees geometry to two O2- atoms. Both N–O bond lengths are 1.23 Å. In the fifth N+2.50+ site, N+2.50+ is bonded in a bent 120 degrees geometry to two equivalent O2- atoms. Both N–O bond lengths are 1.23 Å. There are eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a single-bond geometry to one Na1+ and one N+2.50+ atom. In the second O2- site, O2- is bonded in a single-bond geometry to one Na1+ and one N+2.50+ atom. In the third O2- site, O2- is bonded in a single-bond geometry to one Na1+ and one N+2.50+ atom. In the fourth O2- site, O2- is bonded in a single-bond geometry to one Na1+ and one N+2.50+ atom. In the fifth O2- site, O2- is bonded in a single-bond geometry to one Na1+ and one N+2.50+ atom. In the sixth O2- site, O2- is bonded in a single-bond geometry to one Na1+ and one N+2.50+ atom. In the seventh O2- site, O2- is bonded in a distorted single-bond geometry to one Na1+ and one N+2.50+ atom. In the eighth O2- site, O2- is bonded in a distorted single-bond geometry to one Na1+ and one N+2.50+ atom.
36 MATERIALS SCIENCE↗