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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Rb 4 CuSb 2 Cl 11 and Rb 2 In 0.91(0.2) Sb 0.09 Cl 5 ·H 2 O: Wide Band Gap 0D Metal Halide Semiconductors

Herein, we report the discovery, structural and photophysical characterization of a new zero-dimensional (0D) lead-free all-inorganic halide, Rb 4 CuSb 2 Cl 11 , which adopts a new structure type. Single-crystal X-ray diffraction (SCXRD) shows that the structure consists of isolated, distorted seesaw [SbCl 4 ] − and trigonal planar [CuCl 3 ] 2− units, separated by Rb + cations that provide charge balance. Optoelectronic measurements and density functional theory (DFT) calculations indicate an indirect band gap of 2.89 eV, making it a candidate for wide-bandgap optoelectronic applications. Electrical resistivity was measured at 1.29 × 10 10 Ω·cm, and the trap-state density (n trap ) was found to be 7.44 × 10 10 cm −3 . Attempts to synthesize substitution analogs of Rb 4 CuSb 2 Cl 11 led to the synthesis of Rb 2 In 0.91(0.2) Sb 0.09 Cl 5 ·H 2 O, which was erroneously reported as Rb 2 SbCl 5 O in a previous study. Rb 2 In 0.91(0.2) Sb 0.09 Cl 5 ·H 2 O adopts a vacancyordered perovskite structure and exhibits broad-band yellow emission under UV excitation. The measured photoluminescence quantum yield (PLQY) for Rb 2 In 0.91 (0.2)Sb 0.09 Cl 5 ·H 2 O is 18.2%. These findings add to the growing class of quaternary metal halides with multiple cation and anion compositions, expanding the chemical phase space for the discovery of new materials with functional properties.

Crystal structure↗
DOE OSTI2023

Temperature Dependence of Nuclear Quadrupole Resonance and the Observation of Metal–Ligand Covalency in Actinide Complexes: 35 Cl in Cs 2 UO 2 Cl 4

We report a study of the temperature dependence of 35 Cl nuclear quadrupole resonance (NQR) transition energies and spin–lattice relaxation times (T 1 ) for 235 U-depleted dicesium uranyl tetrachloride (Cs 2 UO 2 Cl 4 ) aimed at elucidating electronic interactions between the uranium center and atoms in the equatorial plane of the UO 2 2+ ion. The transition frequency decreases slowly with temperature below 75 K and with a more rapid linear dependence above this temperature. The spin–lattice relaxation time becomes shorter with temperature, and as temperatures increase, the T 1 decrease becomes nearly quadratic. The observed trends are reproduced by a model that assumes phonon-induced fluctuations of the electric field gradient tensor and partial electron delocalization from Cl to U. The fit of the theoretical model to experimental data allows a Debye temperature of 96 K to be estimated. Finally, the generalization of this approach to investigations of covalency in actinide–ligand bonding is examined.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Equatorial Electronic Structure in the Uranyl Ion: Cs 2 UO 2 Cl 4 and Cs 2 UO 2 Br 4

Electric field gradient (EFG) tensors in the equatorial plane of the linear UO 2 2+ ion have been measured by nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) experiments and computed by relativistic Kohn–Sham methods with and without environment embedding for Cs 2 UO 2 Cl 4 and Cs 2 UO 2 Br 4 . This approach expands the possibilities for probing the electronic structure in uranyl complexes beyond the strongly covalent U–O bonds. The combined analyses find that one of the two largest principal EFG tensor components at the halogen sites points along the U–X bond (X = Cl, Br), and the second is parallel to the UO 2 2+ ion; in Cs 2 UO 2 Cl 4 , the components are nearly equal in magnitude, whereas in Cs 2 UO 2 Br 4 , due to short-range bromide–cesium interactions, the equatorial component is dominant for one pair of Br sites and the axial component is larger for the second pair. Additionally, the directions and relative magnitudes of the field gradient principal axes are found to be sensitive to the σ and π electron donation by the ligands and the model of the environment. Chlorine-35 NQR spectra of 235 U-depleted and 235 U-enriched Cs 2 UO 2 Cl 4 exhibited no uranium-isotope-dependent shift, but the resonance of the depleted sample displayed a 58% broader line width.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Radiation-induced reaction kinetics of Zn 2+ with e S - and Cl 2 ˙ - in Molten LiCl–KCl eutectic at 400–600 °C

We report molten chloride salts are currently under consideration as combined coolant and liquid fuel for next-generation molten salt nuclear reactors. Unlike complementary light-water reactor technologies, the radiation science underpinning molten salts is in its infancy, and thus requires a fundamental mechanistic investigation to elucidate the radiation-driven chemistry within molten salt reactors. Here we present an electron pulse radiolysis kinetics study into the behaviour of the primary radiolytic species generated in molten chloride systems, i.e., the solvated electron (e S - ) and di-chlorine radical anion (Cl 2 ˙- ). We examine the reaction of e S - with Zn 2+ from 400–600 °C (E a = 30.31 ± 0.09 kJ mol -1 ), and the kinetics and decay mechanisms of Cl 2 ˙- in molten lithium chloride-potassium chloride (LiCl–KCl) eutectic. In the absence of Zn 2+ , the lifetime of e S - was found to be dictated by residual impurities in ostensibly “pure” salts, and thus the observed decay is dependent on sample history rather than being an intrinsic property of the salt. The decay of Cl 2 ˙- is complex, owing to the competition of Cl 2 ˙- disproportionation with several other chemical pathways, one of which involves reduction by radiolytically-produced Zn + species. Overall, the reported findings demonstrate the richness and complexity of chemistry involving the interactions of ionizing radiation with molten salts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2026

Colloidal Synthesis of Palladium Nanocluster‐Decorated Cs 3 Sb 2 Cl 9 Perovskite Heterostructural Nanorods for Enhanced CO 2 Photoreduction

Developing efficient and sustainable photocatalysts for CO 2 reduction remains a significant challenge, particularly with environmentally benign materials. Here, in this study, we report the first one-step synthesis of metal–lead-free perovskite heterostructural nanocrystals by decorating Cs 3 Sb 2 Cl 9 perovskite nanorods with size-controlled Pd nanoclusters via a one-step hot-injection method. The resulting Pd-Cs 3 Sb 2 Cl 9 heteronanorods (HNRs) exhibit strong interfacial electronic coupling, enhanced charge separation, and excellent colloidal stability. Transient absorption spectroscopy and DFT calculations reveal a built-in electric field that drives directional electron transfer from the perovskite host to the Pd domains. Under UV irradiation, the Pd-Cs 3 Sb 2 Cl 9 HNRs demonstrate excellent CO 2 photoreduction activity with high CH 4 selectivity, achieving a record apparent quantum yield (AQY) of 2.62% among halide perovskite nanocrystal-based systems with a large electronic yield of 689.3 ± 12.2 µmol·g cat −1 . In situ spectroscopic monitoring and Gibbs free energy analysis further unveil a Pd-facilitated reaction pathway involving stabilization of key intermediates. This work introduces a new class of lead-free perovskite-based heterostructures through a facile one-step synthesis strategy and offers a new design principle for next-generation photocatalysts for solar fuel production.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2023

Organo‐Functionalized Lacunary Double Cubane‐Type Oxometallates: Synthesis, Structure, and Properties of [(M II Cl) 2 (V IV O) 2 {((HOCH 2 CH 2 )(H)N(CH 2 CH 2 O))(HN(CH 2 CH 2 O) 2 )} 2 ] (M=Co, Zn)

Abstract Organofunctionalized tetranuclear clusters [(M II Cl) 2 (V IV O) 2 {((HOCH 2 CH 2 )(H)N(CH 2 CH 2 O))(HN(CH 2 CH 2 O) 2 )} 2 ] (1, M=Co,2: M=Zn) containing an unprecedented oxometallacyclic {M 2 V 2 Cl 2 N 4 O 8 } (M=Co, Zn) framework have been prepared by solvothermal reactions. The new oxo‐alkoxide compounds were fully characterized by spectroscopic methods, magnetic susceptibility measurement, DFT and ab initio computational methods, and complete single‐crystal X‐ray diffraction structure analysis. The isostructural clusters are formed of edge‐sharing octahedral {VO 5 N} and trigonal bipyramidal {MO 3 NCl} units. Diethanolamine ligates the bimetallic lacunary double cubane core of1and2in an unusual two‐mode fashion, unobserved previously. In the crystalline state, the clusters of1and2are joined by hydrogen bonds to form a three‐dimensional network structure. Magnetic susceptibility data indicate weakly antiferromagnetic interactions between the vanadium centers [J iso (V IV −V IV )=−5.4(1); −3.9(2) cm −1 ], and inequivalent antiferromagnetic interactions between the cobalt and vanadium centers [J iso (V IV −Co II )=−12.6 and −7.5 cm −1 ] contained in1.

Chemistry↗
DOE OSTI2023

Li 2 MnO 3 : A Catalyst for a Liquid Cl 2 Electrode in Low‐Temperature Aqueous Batteries

Abstract Li 2 MnO 3 has been contemplated as a high‐capacity cathode candidate for Li‐ion batteries; however, it evolves oxygen during battery charging under ambient conditions, which hinders a reversible reaction. However, it is unclear if this irreversible process still holds under subambient conditions. Here, the low‐temperature electrochemical properties of Li 2 MnO 3 in an aqueous LiCl electrolyte are evaluated and a reversible discharge capacity of 302 mAh g −1 at a potential of 1.0 V versus Ag/AgCl at −78 °C with good rate capability and stable cycling performance, in sharp contrast to the findings in a typical Li 2 MnO 3 cell cycled at room temperature, is observed. However, the results reveal that the capacity does not originate from the reversible oxygen oxidation in Li 2 MnO 3 but the reversible Cl 2 (l)/Cl − (aq.) redox from the electrolyte. The results demonstrate the good catalytic properties of Li 2 MnO 3 to promote the Cl 2 /Cl − redox at low temperatures.

Sui, Yiming↗
DOE OSTI2021

Thermodynamic modeling of calcium carbonate scale precipitation: aqueous Na + -Ca 2+ -Cl – -HCO 3 – -CO 3 2– -CO 2 system

To allow for accurate calculations of calcium carbonate scaling in highly saline produced waters, we present a comprehensive thermodynamic model based on the electrolyte nonrandom two-liquid (eNRTL) activity coefficient equation for the aqueous Na ⁺ -Ca ²⁺ -Cl – -HCO 3 – -CO 3 ²– -CO 2 system. The eNRTL binary interaction parameters for the H 2 O:(Na ⁺ -CO 3 2– ) pair, the H 2 O:(Na ⁺ -HCO 3 – ) pair, the (Na⁺-Cl–):(Na ⁺ -CO 3 2– ) pair, and the (Na ⁺ -Cl – ):(Na ⁺ -HCO 3 – ) pair are identified in this work via the regression of thermodynamic, calorimetric, and phase equilibria experimental data. The binary interaction parameters associated with the H 2 O:(Na ⁺ -Cl – ) pair, the CO 2 :(Na ⁺ -Cl – ) pair, the H 2 O:(Ca ²⁺ -Cl – ) pair, and the (Na ⁺ -Cl – ):(Ca ²⁺ -Cl – ) pair are retrieved from the literature. The remaining binary interaction parameters are retrieved from Aspen Plus or set to zero. In addition, the solubility product constants are identified for Na 2 CO 3 ·10H 2 O (s) , Na 2 CO 3 · 7H 2 O (s) , Na 2 CO 3 ·H 2 O (s) , Na 2 CO 3 ·NaHCO 3 2H 2 O (s) , Na 2 CO 3 ·3NaHCO 3 (s) , and CaCO 3(s) via regression of solubility data. Here, the model is capable of accurately calculating all phase equilibria and calorimetric properties at temperatures up to 473.15 K and salt concentrations up to saturation.

42 ENGINEERING↗
DOE OSTI2020

Spinon excitations in the quasi-one-dimensional $S = \frac{1}{2}$ chain compound Cs 4 CuSb 2 Cl 12

The spin-$\frac{1}{2}$ Heisenberg antiferromagnetic chain is ideal for realizing one of the simplest gapless quantum spin liquids (QSLs), supporting a many-body ground state whose elementary excitations are fractional fermionic excitations called spinons. Here we report the discovery of such a one-dimensional (1D) QSL in Cs 4 CuSb 2 Cl 12 . Compared to previously reported $S = \frac{1}{2}$ 1D chains, this material possesses a wider temperature range over which the QSL state is stabilized. In this work, we identify spinon excitations extending at $\textit{T}$ > 0.8 K, with a large $\textit{T}$-linear contribution to the specific heat, γ = 31.5(2)mJ mol –1 K –2 , which contribute itinerantly to thermal transport up to temperatures as high as $\textit{T}$ = 35 K. At $\textit{T}$ = 0.7 K , we find a second-order phase transition that is unchanged by a $μ_0H = 5T$ magnetic field. Cs 4 CuSb 2 Cl 12 reveals new phenomenology deep in the 1D QSL regime, supporting a gapped QSL phase over a wide temperature range compared to many other experimental realizations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Tunable Perovskite-Derived Bismuth Halides: Cs 3 Bi 2 (Cl 1– x I x ) 9

Bismuth-based perovskites are of interest as safer alternatives to lead-based optoelectronic materials. Prior studies have reported on the compounds Cs 3 Bi 2 Cl 9 , Cs 3 Bi 2 I 9 , and Cs 3 Bi 2 Cl 3 I 6 . Here we examine a range of compounds of the formula Cs 3 Bi 2 (Cl 1–x I x ) 9 , where x takes values from 0.09 to 0.52. Powder and single-crystal X-ray diffraction were used to determine that all of these compounds adopt the layered vacancy-ordered perovskite structure observed for Cs 3 Bi 2 Cl 3 I 6 , which is also the high-temperature phase of Cs 3 Bi 2 Cl 9 . We find that, even with very small iodine incorporation, the structure is switched to that of Cs 3 Bi 2 Cl 3 I 6 , with I atoms displaying a distinct preference for the capping sites on the BiX 6 octahedra. Optical absorption spectroscopy was employed to study the evolution of optical properties of these materials, and this is complemented by density functional theory electronic structure calculations. Finally, three main absorption features were observed for these compounds, and with increasing x, the lowest-energy features are red-shifted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Si–Cl Bond Activations at Ni(0) to Give Bimetallic Ni(I) μ 1,2 -Cl–SiR 1 R 2 Complexes that Undergo Selective Hydrogenolyses to R 1 R 2 SiH 2 Dihydrosilanes

Chlorosilanes are cheap and abundant raw materials as crucial building blocks in silicon chemistry, yet the metal-mediated activation and functionalization of Si–Cl bonds typically require precious metal sources due to their thermodynamic inertness. Herein, we report the stoichiometric, facile activation, and hydrogenolysis of chlorosilanes mediated by a series of low-valent NHC–Ni (NHC = N-heterocyclic carbene) complexes. Treatment of a Ni(0) complex (IPr)Ni(η 6 -toluene) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene) with chlorosilanes (R 1 R 2 SiCl 2 , R 1 = Cl, R 2 = Cl, Me, Ph, or R 1 = R 2 = Me, Et, Ph, 4-MePh) rapidly afforded di-Ni(I) complexes with a bridging silyl ligand ([(IPr)Ni] 2 (μ-SiR 1 R 2 Cl)(μ-Cl), 1 R1,R2 ) in high yields. Use of a bulkier chlorosilane, Ph 2 SiCl 2 , allowed the isolation of the mono-Ni(II) silyl complex (IPr)Ni(SiPh 2 Cl)Cl (2 Ph ) as an intermediate generated via Si–Cl oxidative addition, which underwent comproportionation with (IPr)Ni(η 6 -toluene) to form 1 Ph,Ph in nearly quantitative yield. Interestingly, 1 R1,R2 was found to react with H 2 at room temperature to form mono- or di-hydrosilanes in moderate to high yields, and the product selectivity was found to be highly dependent on the identity of substituents on Si. In conclusion, these results demonstrate a novel example of facile Si–Cl activation and hydrogenolysis mediated by low-valent mono- and dinuclear NHC–Ni complexes under mild conditions.

Liu, Tianchang [University of California, Berkeley↗
DOE OSTI2020

Impacts of hydrogen bonding interactions with Np(v/vi)O 2 Cl 4 complexes: vibrational spectroscopy, redox behavior, and computational analysis

The neptunyl (Np(V)O 2 + /Np(VI)O 2 2+ ) cation is the dominant form of 237 Np in acidic aqueous solutions and the stability of the Np(V) and Np(VI) species is driven by the specific chemical constituents present in the system. Hydrogen bonding with the oxo group may impact the stability of these species, but there is limited understanding of how these intermolecular interactions influence the behavior of both solution and solid-state species. In the current study, we systematically evaluate the interactions between the neptunyl tetrachloride species and hydrogen donors in coordination complexes and in the related aqueous solutions. Both Np(V) compounds (N 2 C 4 H 12 ) 2 [Np(V)O 2 Cl 4 ]Cl (Np(V)pipz) and (NOC 4 H 10 ) 3 [Np(V)O 2 Cl 4 ] (Np(V)morph) exhibit directional hydrogen bonding to the neptunyl oxo group while Np(VI) compounds (NC 5 H 6 ) 2 [Np(VI)O 2 Cl 4 ] (Np(VI)pyr) and (NOC 4 H 10 ) 4 [Np(VI)O 2 Cl 4 ]·2Cl (Np(VI)morph) assemble via halogen interactions. Here, the Raman spectra of the solid-state phases indicate the activation of vibrational bands when there is asymmetry of the neptunyl bond, while these spectral features are not observed within the related solution phase spectra. Density functional theory calculations of the Np(V)pipz system suggest that activation of the ν 3 asymmetric stretch and other combination modes lead to additional complexity within the solid-state spectra. Electrochemical analyses of complexes in the solution phases are consistent with the results of the crystallization experiments as the voltammetric potentials of Np(V)/Np(VI) complexes in the presence of protonated heterocycles differ from the potentials of pure Np(V) and may correlate with the hydrogen bonding interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Emergence of unconventional spin glass-like state in κ–(ET) 2 Cu[N(CN) 2 ]Cl by introducing weak randomness

Recently, Urai et al. reported that an antiferromagnetic long-range-ordered state in κ-(ET) 2 Cu[N(CN) 2 ]Cl changes into a quantum spin liquid via an unconventional spin glass-like state as randomness is introduced by x-ray irradiation. In this work, we focused on the spin glass-like state and conducted a detailed investigation into it using 13 C-NMR measurements on 150-h x-ray-irradiated κ-(ET) 2 Cu[N(CN) 2 ]Cl. We found that the spin glass-like state is composed of two components: the major component inherits the spin structure of nonirradiated κ-(ET) 2 Cu[N(CN) 2 ]Cl, whereas the minor component differs from that of nonirradiated κ-(ET) 2 Cu[N(CN) 2 ]Cl. We also found that in the spin glass-like state, spin moments fluctuate very slowly around stable directions even at low temperatures, which is very likely related to the Griffiths physics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Magnetic structure and magnetoelectric coupling in the antiferromagnet Co 5⁢ (Te⁢O 3 ) 4 ⁢Cl 2

The van der Waals (vdW) layered multiferroics, which host simultaneous ferroelectric and magnetic orders, have attracted attention not only for their potentials to be utilized in nanoelectric devices and spintronics, but also offer alternative opportunities for emergent physical phenomena. To date, the vdW layered multiferroic materials are still very rare. In this work, we have investigated the magnetic structure and magnetoelectric (ME) effects in Co 5 ⁢(Te⁢O 3 ) 4 ⁢Cl 2 , a promising multiferroic compound with antiferromagnetic (AFM) Néel point T N ~18 K. The neutron-powder diffraction reveals the noncoplanar AFM state with preferred Néel vector along the c axis, while a spin reorientation occurring between 8 and 15 K is identified, which results from the distinct temperature dependence of the nonequivalent Co site's moment in Co 5 ⁢(Te⁢O 3 ) 4 ⁢Cl 2 . Moreover, it is found that Co 5 ⁢(Te⁢O 3 ) 4 ⁢Cl 2 is one of the best vdW multiferroics studied so far in terms of the multiferroic performance. The measured linear ME coefficient exhibits the emergent oscillation dependence of the angle between magnetic field and electric field, and the maximal value is as big as 45 ps/m. Finally, it is suggested that Co 5 ⁢(Te⁢O 3 ) 4 ⁢Cl 2 is an appreciated platform for exploring the emergent multiferroicity in vdW layered compounds.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Crystal growth, density functional theory, and scintillation properties of Tl 3 LnCl 6 :Ce 3+ and TlLn 2 Cl 7 :Ce 3+ (Ln = Y, Gd)

In this paper we report on the crystal growth, density functional theory (DFT) calculations and scintillation properties of Tl 3 LnCl 6 :Ce and TlLn 2 Cl 7 :Ce(Ln = Y, Gd). Crystals were grown by the Vertical Bridgman technique up to 16 mm in diameter and 25 mm long. Crystals of Tl 3 YCl 6 :Ce and Tl 3 GdCl 6 :Ce belong to the family of the Nesohalides which have the monoclinic crystal structure. Crystals of TlY 2 Cl 7 :Ce and TlGd 2 Cl 7 :Ce belong to the family of the Phyllohalides which have either the monoclinic or the orthorhombic crystal structure. We report the light yields of these Nesohalides and Phyllohalides are typically on the order of 35,000–40,000 ph/MeV.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗