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DOE OSTI2020

Materials Data on CsTlAgF6 by Materials Project

CsAgTlF6 crystallizes in the orthorhombic Imma space group. The structure is three-dimensional. Cs1+ is bonded to five F1- atoms to form distorted CsF5 square pyramids that share corners with four equivalent AgF6 octahedra and corners with six equivalent TlF6 octahedra. The corner-sharing octahedra tilt angles range from 64–67°. There are four shorter (3.35 Å) and one longer (3.51 Å) Cs–F bond lengths. Ag2+ is bonded to six F1- atoms to form AgF6 octahedra that share corners with two equivalent AgF6 octahedra, corners with four equivalent TlF6 octahedra, and corners with four equivalent CsF5 square pyramids. The corner-sharing octahedra tilt angles range from 35–49°. There are two shorter (2.06 Å) and four longer (2.32 Å) Ag–F bond lengths. Tl3+ is bonded to six F1- atoms to form TlF6 octahedra that share corners with two equivalent TlF6 octahedra, corners with four equivalent AgF6 octahedra, and corners with six equivalent CsF5 square pyramids. The corner-sharing octahedra tilt angles range from 46–49°. There are four shorter (2.18 Å) and two longer (2.26 Å) Tl–F bond lengths. There are three inequivalent F1- sites. In the first F1- site, F1- is bonded in a 2-coordinate geometry to one Cs1+ and two equivalent Tl3+ atoms. In the second F1- site, F1- is bonded in a bent 150 degrees geometry to two equivalent Ag2+ atoms. In the third F1- site, F1- is bonded in a 3-coordinate geometry to one Cs1+, one Ag2+, and one Tl3+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Reactivities of Interstitial Hydrides in a Cu 11 Template: En Route to Bimetallic Clusters

In sharp contrast to surface hydrides, reactivities of interstitial hydrides are difficult to explore. When treated with a metal ion (Cu + , Ag + , and Au + ), the stable CuI dihydride template [Cu 11 H 2 {S 2 P(OiPr) 2 } 6 (C≡CPh) 3 ] (H 2 Cu 11 ) generates surprisingly three very different compounds, namely [CuH 2 Cu 11 {S 2 P(OiPr) 2 } 6 (C≡CPh) 3 ] + (1), [AgH 2 Cu 14 {S 2 P(OiPr) 2 } 6 ((C≡CPh) 6 ] + (2), and [AuCu 11 {S 2 P(OiPr) 2 } 6 (C≡CPh) 3 Cl] (3). Compounds 1 and 2 are both MI species and maintain the same number of hydride ligands as their H 2 Cu 11 precursor. Neutron diffraction revealed the first time a trigonal-pyramidal hydride coordination mode in the AgCu 3 environment of 2. 3 has no hydride and exhibits a mixed-valent [AuCu 11 ] 10+ metal core, making it a two-electron superatom.

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

Hydrogen bonds and dispersion forces serving as molecular locks for tailored Group 11 bis(amidine) complexes

A flexible polydentate bis(amidine) ligand LH 2 , LH 2 = {CH 2 NH( t Bu)C=N-2-(6-MePy)} 2 , operates as a molecular lock for various coinage metal fragments and forms the dinuclear complexes [LH 2 (MCl) 2 ], M = Cu (1), Au (2), the coordination polymer [{(LH 2 ) 2 (py) 2 (AgCl) 3 }(py) 3 ] n (3), and the dimesityl-digold complex [LH 2 (AuMes) 2 ] (4) by formal insertion of MR fragments (M = Cu, Ag, Au; R = Cl, Mes) into the N–H∙∙∙N hydrogen bonds of LH 2 in yields of 43–95%. Complexes 1, 2, and 4 adopt C 2 -symmetrical structures in the solid state featuring two interconnected 11-membered rings that are locked by two intramolecular N–H∙∙∙R–M hydrogen bonds. QTAIM analyses of the computational geometry-optimized structures 1a, 2a, and 4a reveal 13, 11, and 22 additional bond critical points, respectively, all of which are related to weak intramolecular attractive interactions, predominantly representing dispersion forces, contributing to the conformational stabilization of the C2-symmetrical stereoisomers in the solid state. Variable-temperature 1 H NMR spectroscopy in combination with DFT calculations indicate a dynamic conformational interconversion between two C 2 -symmetrical ground state structures in solution (ΔG ‡ c = 11.1–13.8 kcal mol –1 ), which is accompanied by the formation of an intermediate possessing C i symmetry that retains the hydrogen bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Materials Data on Ag3(Bi2Br3)7 by Materials Project

(AgBi4Br7)3(Bi)2 crystallizes in the monoclinic Pm space group. The structure is three-dimensional and consists of four bismuth molecules and one AgBi4Br7 framework. In the AgBi4Br7 framework, there are three inequivalent Ag1+ sites. In the first Ag1+ site, Ag1+ is bonded to six Br1- atoms to form distorted AgBr6 octahedra that share a cornercorner with one AgBr6 octahedra, an edgeedge with one AgBr6 octahedra, and edges with three BiBr6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are a spread of Ag–Br bond distances ranging from 2.68–3.18 Å. In the second Ag1+ site, Ag1+ is bonded to six Br1- atoms to form distorted AgBr6 octahedra that share a cornercorner with one AgBr6 octahedra, edges with two AgBr6 octahedra, and edges with two BiBr6 octahedra. The corner-sharing octahedral tilt angles are 63°. There are a spread of Ag–Br bond distances ranging from 2.67–3.33 Å. In the third Ag1+ site, Ag1+ is bonded to six Br1- atoms to form distorted AgBr6 octahedra that share a cornercorner with one AgBr6 octahedra, an edgeedge with one AgBr6 octahedra, and edges with three BiBr6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are a spread of Ag–Br bond distances ranging from 2.74–3.12 Å. There are fifteen inequivalent Bi+1.29+ sites. In the first Bi+1.29+ site, Bi+1.29+ is bonded in a 3-coordinate geometry to three Br1- atoms. There are two shorter (3.55 Å) and one longer (3.59 Å) Bi–Br bond lengths. In the second Bi+1.29+ site, Bi+1.29+ is bonded to six Br1- atoms to form BiBr6 octahedra that share a cornercorner with one BiBr6 octahedra, edges with two AgBr6 octahedra, and edges with two BiBr6 octahedra. The corner-sharing octahedral tilt angles are 43°. There are a spread of Bi–Br bond distances ranging from 2.78–3.01 Å. In the third Bi+1.29+ site, Bi+1.29+ is bonded in a 3-coordinate geometry to three Br1- atoms. There are a spread of Bi–Br bond distances ranging from 3.43–3.57 Å. In the fourth Bi+1.29+ site, Bi+1.29+ is bonded in a 3-coordinate geometry to three Br1- atoms. There are two shorter (3.32 Å) and one longer (3.52 Å) Bi–Br bond lengths. In the fifth Bi+1.29+ site, Bi+1.29+ is bonded to six Br1- atoms to form BiBr6 octahedra that share a cornercorner with one BiBr6 octahedra, an edgeedge with one BiBr6 octahedra, and edges with three AgBr6 octahedra. The corner-sharing octahedral tilt angles are 50°. There are a spread of Bi–Br bond distances ranging from 2.81–3.05 Å. In the sixth Bi+1.29+ site, Bi+1.29+ is bonded in a 3-coordinate geometry to three Br1- atoms. There are a spread of Bi–Br bond distances ranging from 3.33–3.53 Å. In the seventh Bi+1.29+ site, Bi+1.29+ is bonded in a square co-planar geometry to four Br1- atoms. There are two shorter (2.88 Å) and two longer (2.91 Å) Bi–Br bond lengths. In the eighth Bi+1.29+ site, Bi+1.29+ is bonded in an L-shaped geometry to two Br1- atoms. There are one shorter (3.02 Å) and one longer (3.35 Å) Bi–Br bond lengths. In the ninth Bi+1.29+ site, Bi+1.29+ is bonded in a single-bond geometry to one Br1- atom. The Bi–Br bond length is 3.31 Å. In the tenth Bi+1.29+ site, Bi+1.29+ is bonded in a rectangular see-saw-like geometry to four Br1- atoms. There are two shorter (2.95 Å) and two longer (2.99 Å) Bi–Br bond lengths. In the eleventh Bi+1.29+ site, Bi+1.29+ is bonded in a 2-coordinate geometry to two Br1- atoms. There are one shorter (3.04 Å) and one longer (3.40 Å) Bi–Br bond lengths. In the twelfth Bi+1.29+ site, Bi+1.29+ is bonded to six Br1- atoms to form BiBr6 octahedra that share a cornercorner with one BiBr6 octahedra, an edgeedge with one BiBr6 octahedra, and edges with three AgBr6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are a spread of Bi–Br bond distances ranging from 2.76–3.16 Å. In the thirteenth Bi+1.29+ site, Bi+1.29+ is bonded in a 1-coordinate geometry to four Br1- atoms. There are a spread of Bi–Br bond distances ranging from 3.25–3.57 Å. In the fourteenth Bi+1.29+ site, Bi+1.29+ is bonded in a 5-coordinate geometry to five Br1- atoms. There are a spread of Bi–Br bond distances ranging from 2.89–3.26 Å. In the fifteenth Bi+1.29+ site, Bi+1.29+ is bonded in a 3-coordinate geometry to three Br1- atoms. There are one shorter (3.43 Å) and two longer (3.50 Å) Bi–Br bond lengths. There are twenty-six inequivalent Br1- sites. In the first Br1- site, Br1- is bonded in an L-shaped geometry to two Bi+1.29+ atoms. In the second Br1- site, Br1- is bonded in a 10-coordinate geometry to two equivalent Bi+1.29+ atoms. In the third Br1- site, Br1- is bonded in a 3-coordinate geometry to one Ag1+ and two Bi+1.29+ atoms. In the fourth Br1- site, Br1- is bonded in a 2-coordinate geometry to four Bi+1.29+ atoms. In the fifth Br1- site, Br1- is bonded in a 2-coordinate geometry to two equivalent Bi+1.29+ atoms. In the sixth Br1- site, Br1- is bonded in a bent 120 degrees geometry to two equivalent Bi+1.29+ atoms. In the seventh Br1- site, Br1- is bonded in a distorted T-shaped geometry to one Ag1+ and two Bi+1.29+ atoms. In the eighth Br1- site, Br1- is bonded in a 1-coordinate geometry to four Bi+1.29+ atoms. In the ninth Br1- site, Br1- is bonded in a distorted L-shaped geometry to one Ag1+ and two Bi+1.29+ atoms. In the tenth Br1- site, Br1- is bonded in a distorted L-shaped geometry to one Ag1+ and two Bi+1.29+ atoms. In the eleventh Br1- site, Br1- is bonded in a bent 120 degrees geometry to two equivalent Ag1+ atoms. In the twelfth Br1- site, Br1- is bonded in a distorted trigonal non-coplanar geometry to two Ag1+ and one Bi+1.29+ atom. In the thirteenth Br1- site, Br1- is bonded in a 3-coordinate geometry to three Bi+1.29+ atoms. In the fourteenth Br1- site, Br1- is bonded in a 4-coordinate geometry to four Bi+1.29+ atoms. In the fifteenth Br1- site, Br1- is bonded in a 3-coordinate geometry to two Ag1+ and one Bi+1.29+ atom. In the sixteenth Br1- site, Br1- is bonded in a bent 120 degrees geometry to two equivalent Ag1+ and one Bi+1.29+ atom. In the seventeenth Br1- site, Br1- is bonded in an L-shaped geometry to one Ag1+ and one Bi+1.29+ atom. In the eighteenth Br1- site, Br1- is bonded in a distorted T-shaped geometry to two Ag1+ and one Bi+1.29+ atom. In the nineteenth Br1- site, Br1- is bonded in a 3-coordinate geometry to four Bi+1.29+ atoms. In the twentieth Br1- site, Br1- is bonded in a distorted trigonal non-coplanar geometry to two Ag1+ and one Bi+1.29+ atom. In the twenty-first Br1- site, Br1- is bonded in a bent 120 degrees geometry to two equivalent Bi+1.29+ atoms. In the twenty-second Br1- site, Br1- is bonded in an L-shaped geometry to two equivalent Bi+1.29+ atoms. In the twenty-third Br1- site, Br1- is bonded in a 4-coordinate geometry to two equivalent Ag1+ and two Bi+1.29+ atoms. In the twenty-fourth Br1- site, Br1- is bonded in a 3-coordinate geometry to one Ag1+ and two Bi+1.29+ atoms. In the twenty-fifth Br1- site, Br1- is bonded in a 2-coordinate geometry to four Bi+1.29+ atoms. In the twenty-sixth Br1- site, Br1- is bonded in a distorted T-shaped geometry to one Ag1+ and two Bi+1.29+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on CsInAgF6 by Materials Project

CsAgInF6 crystallizes in the orthorhombic Imma space group. The structure is three-dimensional. Cs1+ is bonded to six F1- atoms to form CsF6 octahedra that share corners with six equivalent AgF6 octahedra and corners with six equivalent InF6 octahedra. The corner-sharing octahedra tilt angles range from 65–71°. There are a spread of Cs–F bond distances ranging from 3.32–3.66 Å. Ag2+ is bonded to six F1- atoms to form AgF6 octahedra that share corners with two equivalent AgF6 octahedra, corners with four equivalent InF6 octahedra, and corners with six equivalent CsF6 octahedra. The corner-sharing octahedra tilt angles range from 39–71°. There are two shorter (2.07 Å) and four longer (2.33 Å) Ag–F bond lengths. In3+ is bonded to six F1- atoms to form InF6 octahedra that share corners with two equivalent InF6 octahedra, corners with four equivalent AgF6 octahedra, and corners with six equivalent CsF6 octahedra. The corner-sharing octahedra tilt angles range from 38–71°. There are four shorter (2.10 Å) and two longer (2.14 Å) In–F bond lengths. There are three inequivalent F1- sites. In the first F1- site, F1- is bonded in a bent 150 degrees geometry to one Cs1+ and two equivalent In3+ atoms. In the second F1- site, F1- is bonded in a distorted bent 150 degrees geometry to one Cs1+ and two equivalent Ag2+ atoms. In the third F1- site, F1- is bonded in a 3-coordinate geometry to one Cs1+, one Ag2+, and one In3+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Zr3Cd3AgF20 by Materials Project

Zr3AgCd3F20 crystallizes in the hexagonal P6_3/m space group. The structure is three-dimensional. Zr4+ is bonded to seven F1- atoms to form ZrF7 pentagonal bipyramids that share corners with two equivalent ZrF7 pentagonal bipyramids, corners with four equivalent CdF7 pentagonal bipyramids, an edgeedge with one AgF8 hexagonal bipyramid, and an edgeedge with one CdF7 pentagonal bipyramid. There are a spread of Zr–F bond distances ranging from 2.03–2.14 Å. Ag2+ is bonded to eight F1- atoms to form distorted AgF8 hexagonal bipyramids that share corners with two equivalent AgF8 hexagonal bipyramids, edges with three equivalent ZrF7 pentagonal bipyramids, and edges with three equivalent CdF7 pentagonal bipyramids. There are a spread of Ag–F bond distances ranging from 2.13–2.77 Å. Cd2+ is bonded to seven F1- atoms to form CdF7 pentagonal bipyramids that share corners with four equivalent ZrF7 pentagonal bipyramids, an edgeedge with one AgF8 hexagonal bipyramid, an edgeedge with one ZrF7 pentagonal bipyramid, and edges with two equivalent CdF7 pentagonal bipyramids. There are a spread of Cd–F bond distances ranging from 2.24–2.51 Å. There are seven inequivalent F1- sites. In the first F1- site, F1- is bonded in a linear geometry to two equivalent Zr4+ atoms. In the second F1- site, F1- is bonded in a linear geometry to one Zr4+ and one Cd2+ atom. In the third F1- site, F1- is bonded in a trigonal planar geometry to one Zr4+, one Ag2+, and one Cd2+ atom. In the fourth F1- site, F1- is bonded in a distorted bent 150 degrees geometry to one Zr4+, one Ag2+, and one Cd2+ atom. In the fifth F1- site, F1- is bonded in a linear geometry to two equivalent Ag2+ atoms. In the sixth F1- site, F1- is bonded in a trigonal planar geometry to three equivalent Cd2+ atoms. In the seventh F1- site, F1- is bonded in a 3-coordinate geometry to one Zr4+ and two equivalent Cd2+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on FeAgAs(S2N3)2 by Materials Project

FeAgAs(N3S2)2 crystallizes in the tetragonal P-4n2 space group. The structure is three-dimensional. Fe3+ is bonded in a 4-coordinate geometry to four equivalent N+0.33- atoms. All Fe–N bond lengths are 1.81 Å. Ag2+ is bonded in a 4-coordinate geometry to four equivalent S2- atoms. All Ag–S bond lengths are 2.55 Å. As5+ is bonded in a tetrahedral geometry to four equivalent S2- atoms. All As–S bond lengths are 2.20 Å. There are two inequivalent N+0.33- sites. In the first N+0.33- site, N+0.33- is bonded in a 1-coordinate geometry to one Fe3+, one N+0.33-, and one S2- atom. The N–N bond length is 1.34 Å. The N–S bond length is 2.52 Å. In the second N+0.33- site, N+0.33- is bonded in a water-like geometry to two equivalent N+0.33- atoms. S2- is bonded in a 3-coordinate geometry to one Ag2+, one As5+, and one N+0.33- atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on ZnAgPO4 by Materials Project

AgZnPO4 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. Ag1+ is bonded in a distorted rectangular see-saw-like geometry to four O2- atoms. There are a spread of Ag–O bond distances ranging from 2.33–2.54 Å. Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with four equivalent PO4 tetrahedra. There is one shorter (1.97 Å) and three longer (1.98 Å) Zn–O bond length. P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with four equivalent ZnO4 tetrahedra. There is one shorter (1.55 Å) and three longer (1.56 Å) P–O bond length. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted trigonal planar geometry to one Ag1+, one Zn2+, and one P5+ atom. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to one Ag1+, one Zn2+, and one P5+ atom. In the third O2- site, O2- is bonded in a 3-coordinate geometry to one Ag1+, one Zn2+, and one P5+ atom. In the fourth O2- site, O2- is bonded in a 3-coordinate geometry to one Ag1+, one Zn2+, and one P5+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on K3Hf4Ag2F23 by Materials Project

K3Hf4Ag2F23 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. there are two inequivalent K1+ sites. In the first K1+ site, K1+ is bonded in a 5-coordinate geometry to eight F1- atoms. There are a spread of K–F bond distances ranging from 2.64–3.12 Å. In the second K1+ site, K1+ is bonded in a 6-coordinate geometry to six F1- atoms. There are four shorter (2.71 Å) and two longer (2.91 Å) K–F bond lengths. There are two inequivalent Hf4+ sites. In the first Hf4+ site, Hf4+ is bonded in a 8-coordinate geometry to eight F1- atoms. There are a spread of Hf–F bond distances ranging from 1.99–2.25 Å. In the second Hf4+ site, Hf4+ is bonded in a 8-coordinate geometry to eight F1- atoms. There are a spread of Hf–F bond distances ranging from 2.01–2.27 Å. Ag2+ is bonded in a 5-coordinate geometry to seven F1- atoms. There are a spread of Ag–F bond distances ranging from 2.10–2.73 Å. There are twelve inequivalent F1- sites. In the first F1- site, F1- is bonded in a 3-coordinate geometry to one K1+, one Hf4+, and one Ag2+ atom. In the second F1- site, F1- is bonded in a linear geometry to two equivalent Hf4+ atoms. In the third F1- site, F1- is bonded in a bent 120 degrees geometry to two Hf4+ atoms. In the fourth F1- site, F1- is bonded in a distorted trigonal planar geometry to one K1+ and two Hf4+ atoms. In the fifth F1- site, F1- is bonded in a 3-coordinate geometry to one K1+ and two Hf4+ atoms. In the sixth F1- site, F1- is bonded in a 1-coordinate geometry to two K1+, one Hf4+, and one Ag2+ atom. In the seventh F1- site, F1- is bonded in a 3-coordinate geometry to one K1+, one Hf4+, and one Ag2+ atom. In the eighth F1- site, F1- is bonded in a 1-coordinate geometry to one K1+, one Hf4+, and one Ag2+ atom. In the ninth F1- site, F1- is bonded in a 3-coordinate geometry to two K1+, one Hf4+, and one Ag2+ atom. In the tenth F1- site, F1- is bonded in a linear geometry to one Hf4+ and one Ag2+ atom. In the eleventh F1- site, F1- is bonded in a distorted bent 150 degrees geometry to one Hf4+ and one Ag2+ atom. In the twelfth F1- site, F1- is bonded in a 2-coordinate geometry to two equivalent K1+ and two Hf4+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on LiAgF4 by Materials Project

LiAgF4 is zeta iron carbide-derived structured and crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. Li1+ is bonded in a 6-coordinate geometry to six F1- atoms. There are a spread of Li–F bond distances ranging from 1.95–2.59 Å. Ag3+ is bonded to six F1- atoms to form corner-sharing AgF6 octahedra. The corner-sharing octahedra tilt angles range from 41–49°. There are a spread of Ag–F bond distances ranging from 2.05–2.14 Å. There are four inequivalent F1- sites. In the first F1- site, F1- is bonded in a 3-coordinate geometry to one Li1+ and two equivalent Ag3+ atoms. In the second F1- site, F1- is bonded in a distorted trigonal planar geometry to one Li1+ and two equivalent Ag3+ atoms. In the third F1- site, F1- is bonded in a distorted trigonal planar geometry to two equivalent Li1+ and one Ag3+ atom. In the fourth F1- site, F1- is bonded in a trigonal planar geometry to two equivalent Li1+ and one Ag3+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Single-Step Conversion of Ethanol to n-Butene over Ag-ZrO2/SiO2 Catalysts

Ethanol is a promising platform molecule for production of a variety of fuels and chemicals. Of particular interest is producing middle distillate fuels (i.e., jet and diesel blendstock) from renewable ethanol feedstock. State-of-the-art alcohol-to-jet technology requires multiple process steps based on catalytic dehydration of ethanol to form ethylene, followed by sometimes a multi-step oligomerization, and then hydrotreatment and distillation. Here we report on a new catalytic route in which ethanol is directly converted to n-butene (1- and 2-butene mixtures) over Ag-ZrO2/SBA-16, thus offering the potential for a reduction in the number of required processing steps versus conventional alcohol-to-jet technology. This catalyst system provides the balanced metal and Lewis acid sites required to selectively facilitate a cascading sequence of reactions that includes dehydrogenation, aldol condensation, Meerwein–Ponndorf–Verley reduction, dehydration, and hydrogenation. High conversion and selectivity toward either n-butene or 1,3-butadiene is achieved by tuning the hydrogen feed partial pressure and other process/catalyst parameters. With sufficient hydrogen partial pressure 1,3-butadiene is completely and selectively hydrogenated to form n-butene. The reaction mechanism was elucidated through operando-nuclear magnetic resonance investigations coupled with reactivity measurements. Combined experimental-computational investigation reveals how changes in silver and zirconium composition and the silver oxidation state affects reactivity under controlled hydrogen partial pressures and after prolonged run times. Finally, catalyst effectiveness also was demonstrated when using wet ethanol feed, thus highlighting process flexibility in terms of feedstock purity requirements. This work was financially supported by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office, and was performed at the Pacific Northwest National Laboratory (PNNL) under Contract No. DE-AC05-76RL01830 and the National Renewable Energy Laboratory under Contract No. DE-AC36- 08GO28308. Part of the work conducted by S. A. Akhade was performed under the auspices of the U.S. DOE at Lawrence Livermore National Laboratory under Contract No. DE-AC52-07NA27344. This work was partly supported through the PNNL-WSU Distinguished Graduate Research Program for ADW. NMR and XPS experiments were performed using EMSL (grid.436923.9), a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research

Dagle, Vanessa↗
DOE OSTI2022

Silver-Mediated Squaric Acid Reduction as a Facile, Ambient-temperature and Seedless Route to Tunable Bimetallic Au/Ag Nanostars and Nanosnowflakes

In this work, bimetallic Au/Ag nanoparticles were successfully synthesized using a facile and reproducible method involving rapid, room temperature mixing of aqueous solutions of HAuCl 4 and AgNO 3 in the presence of squaric acid as both the reducing agent and surface capping ligand. Variation in the initial Au:Ag molar ratio yielded a tunable anisotropic shape and affiliated surface plasmon resonance. The nanoparticles displayed excellent stability in water for at least 10 weeks and showed robust catalytic activity in the borohydride-assisted reduction of the model substrate 4-nitrophenol.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Surface-Enhanced Raman Detection of the CO 2 Moisture Swing

The development of scalable, energy-efficient carbon dioxide (CO 2 ) capture technologies is critical for achieving net-zero emissions. Moisture swing (MS) sorbents offer a promising alternative to traditional thermal regeneration methods by enabling reversible CO 2 binding through humidity-driven ion hydrolysis. In this study, we investigate the anion speciation dynamics in two classes of MS materials─an anion-exchange resin with a bicarbonate anion and activated carbon impregnated with potassium bicarbonate salt─using both sorption measurements and in situ surface-enhanced Raman spectroscopy (SERS). Ni-coated Ag nanowires were employed as SERS substrates to enhance signal intensity and enable the real-time detection of carbonate (CO 3 2– ), bicarbonate (HCO 3 – ), and hydroxide (OH – ) species under controlled humidity conditions in both air and nitrogen atmospheres. The results reveal humidity-dependent interconversion between anionic species with significant spectral shifts confirming the reversible hydrolysis reactions that drive the MS mechanism. Under humid conditions, we observed the depletion of bicarbonate signals and a concurrent increase in carbonate species, consistent with moisture-induced desorption of CO 2 . With the activated carbon samples, we further observed the formation of hydroxide. These findings not only validate the mechanistic models of humidity-driven anion exchange in MS sorbents but also demonstrate the practical potential of SERS as an operando diagnostic tool for monitoring CO 2 capture media. The ability to resolve and semiquantitatively evaluate the reversible transformation of carbonate, bicarbonate, and hydroxide ions under realistic environmental conditions provides valuable insight for the rational design, performance optimization, and quality control of next-generation sorbent materials for direct air capture applications.

CO2 capture↗
DOE OSTI2023

Make Selenium Reactive Again: Activating Elemental Selenium for Synthesis of Metal Selenides Ranging from Nanocrystals to Large Single Crystals

The inertness of elemental selenium is a significant obstacle in the synthesis of selenium-containing materials at low reaction temperatures. Over the years, several recipes have been developed to overcome this hurdle; however, most of the methods are associated with the use of highly toxic, expensive, and environmentally harmful reagents. As such, there is an increasing demand for the design of cheap, stable, and nontoxic reactive selenium precursors usable in the low-temperature synthesis of transition metal selenides with vast applications in nanotechnology, thermoelectrics, and superconductors. Herein, a novel synthetic route has been developed for activating elemental selenium by using a solvothermal approach. By comprehensive 77 Se NMR, Raman, and infrared spectroscopies and gas chromatography–mass spectrometry, we show that the activated Se solution contained HSe – , [Se–Se] 2– , and Se 2– ions, as well as dialkyl selenide (R 2 Se) and dialkyl diselenide (R–Se–Se–R) species in dynamic equilibrium. This also corresponded to the first observation of naked Se 2 2– in solution. The versatility of the developed Se precursor was demonstrated by the successful synthesis of (i) the polycrystalline room-temperature modification of the β-Ag 2 Se thermoelectric material; (ii) large single crystals of superconducting β-FeSe; (iii) CdSe nanocrystals with different particle sizes (3–10 nm); (iv) nanosheets of PtSe 2 ; and (v) mono- and dibenzyl selenides and diselenides at room temperature. In conclusion, The simplicity and diversity of the developed Se activation method holds promise for applied and fundamental research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Titanium dioxide and table sugar enhance the leaching of silver out of nanosilver packaging

We manufactured laboratory-scale food packages containing 2.57 ± 0.18 × 10 –3 wt% silver nanoparticles (AgNPs) and used them to show that table sugar (sucrose) and microcrystalline titanium dioxide (μTiO 2 ) enhance Ag migration from these packages and into aqueous food simulants. Ag migration into purified water was detected but was below the limit of ICP-MS quantitation, giving a range of potential Ag migration between 0.059 and 0.082 ng cm –2 packaging surface area. Ag migration into 9 wt% aqueous sucrose solution was 0.547 ± 0.084 ng cm –2 and migration into 9 wt% sucrose solution containing 0.01 wt% μTiO 2 was 0.724 ± 0.032 ng cm –2 . Total Ag migration into a 0.01 wt% μTiO 2 aqueous dispersion without sucrose was between 0.122 and 0.162 ng cm –2 , with upper and lower limits defined by the detectability of Ag in the supernatant phase of the simulant. If the midpoint of this range is taken as a baseline, these results imply that, compared to purified water, Ag migration was increased by approximately 10.3 times when the water simulant contained μTiO 2 and sucrose at commercially-relevant concentrations. Notably, the Ag migrated into water containing both ingredients exceeded the total Ag migrated into either of the single-ingredient simulants, pointing to a potential cooperative relationship between sucrose and μTiO 2 that possibly derives from binding and redox interactions between these two ingredients. Sucrose and μTiO 2 also both reduced a portion of migrated Ag + back into AgNPs, and μTiO 2 particles efficiently captured (>25% by mass) migrated Ag on their surfaces. Similar effects on migration were observed with nanocrystalline TiO 2 . Furthermore, these experiments are the first to show that TiO 2 particles exert a strong influence on the quantity and form of Ag that could migrate from AgNP-enabled packaging, suggesting that food formulations and interactions between individual food components may be important to consider when evaluating the fate of nanoparticles in these consumer applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Modeling plasma-induced surface charge effects on CO 2 activation by single atom catalysts supported on reducible and irreducible metal oxides

Abstract The accumulation of negative surface charge on catalytic surfaces in the presence of low-temperature plasma (LTP) could influence catalytic performance. However, it is difficult to disentangle the role of surface charging and other LTP catalytic effects in experiment. Herein, we use density functional theory (DFT) modeling to understand the effect of plasma-induced surface charging on CO 2 activation by atomically dispersed single atom (SA) catalysts on both reducible and irreducible metal oxide supports. We model CO 2 adsorption strength and CO 2 dissociation barriers for Co 1 , Ni 1 , Cu 1 , Rh 1 , Pd 1 , and Ag 1 SAs on both reducible and irreducible supports, namely, CeO 2 (100), TiO 2 (101), and γ -Al 2 O 3 (110), to elucidate trends. We find that accumulated surface charge on the SA increases the CO 2 adsorption strength and decreases the CO 2 dissociation barrier for all studied SA/support combinations. For both charged and uncharged (neutral) systems, SAs on the reducible CeO 2 (100) support generally adsorb CO 2 more weakly compared to when on irreducible supports like γ -Al 2 O 3 (110). SAs on γ -Al 2 O 3 (110) typically have larger barriers for CO 2 dissociation for both charged and uncharged systems compared to TiO 2 (101) and CeO 2 (100). The magnitude of surface charging effects on CO 2 binding energies and dissociation barriers depends sensitively on both the SA and the support. In some cases, the CO 2 activation trends qualitatively change between neutral and charged systems for a fixed SA across different supports. This DFT modeling study demonstrates that surface charging should be considered in strong electric fields because it can have a large effect on molecule adsorption and bond-breaking on catalytic surfaces.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Materials Data on AgH24C9S3N6ClO4 by Materials Project

AgC9H24(N2S)3ClO4 crystallizes in the triclinic P-1 space group. The structure is zero-dimensional and consists of one AgC9H24(N2S)3 cluster and two ClO4 clusters. In the AgC9H24(N2S)3 cluster, Ag1+ is bonded to four S2- atoms to form edge-sharing AgS4 tetrahedra. There are a spread of Ag–S bond distances ranging from 2.54–2.70 Å. There are nine inequivalent C+0.89+ sites. In the first C+0.89+ site, C+0.89+ is bonded in a distorted trigonal planar geometry to two N3- and one S2- atom. Both C–N bond lengths are 1.34 Å. The C–S bond length is 1.73 Å. In the second C+0.89+ site, C+0.89+ is bonded in a tetrahedral geometry to one N3- and three H1+ atoms. The C–N bond length is 1.45 Å. There is one shorter (1.09 Å) and two longer (1.10 Å) C–H bond length. In the third C+0.89+ site, C+0.89+ is bonded in a tetrahedral geometry to one N3- and three H1+ atoms. The C–N bond length is 1.45 Å. All C–H bond lengths are 1.10 Å. In the fourth C+0.89+ site, C+0.89+ is bonded in a distorted trigonal planar geometry to two N3- and one S2- atom. Both C–N bond lengths are 1.34 Å. The C–S bond length is 1.73 Å. In the fifth C+0.89+ site, C+0.89+ is bonded in a tetrahedral geometry to one N3- and three H1+ atoms. The C–N bond length is 1.45 Å. All C–H bond lengths are 1.10 Å. In the sixth C+0.89+ site, C+0.89+ is bonded in a tetrahedral geometry to one N3- and three H1+ atoms. The C–N bond length is 1.45 Å. All C–H bond lengths are 1.10 Å. In the seventh C+0.89+ site, C+0.89+ is bonded in a distorted trigonal planar geometry to two N3- and one S2- atom. Both C–N bond lengths are 1.35 Å. The C–S bond length is 1.71 Å. In the eighth C+0.89+ site, C+0.89+ is bonded in a tetrahedral geometry to one N3- and three H1+ atoms. The C–N bond length is 1.45 Å. There is one shorter (1.09 Å) and two longer (1.10 Å) C–H bond length. In the ninth C+0.89+ site, C+0.89+ is bonded in a tetrahedral geometry to one N3- and three H1+ atoms. The C–N bond length is 1.45 Å. There is one shorter (1.09 Å) and two longer (1.10 Å) C–H bond length. There are six inequivalent N3- sites. In the first N3- site, N3- is bonded in a trigonal planar geometry to two C+0.89+ and one H1+ atom. The N–H bond length is 1.02 Å. In the second N3- site, N3- is bonded in a trigonal planar geometry to two C+0.89+ and one H1+ atom. The N–H bond length is 1.02 Å. In the third N3- site, N3- is bonded in a trigonal planar geometry to two C+0.89+ and one H1+ atom. The N–H bond length is 1.02 Å. In the fourth N3- site, N3- is bonded in a trigonal planar geometry to two C+0.89+ and one H1+ atom. The N–H bond length is 1.03 Å. In the fifth N3- site, N3- is bonded in a trigonal planar geometry to two C+0.89+ and one H1+ atom. The N–H bond length is 1.02 Å. In the sixth N3- site, N3- is bonded in a trigonal planar geometry to two C+0.89+ and one H1+ atom. The N–H bond length is 1.01 Å. There are twenty-four inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the second H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the third H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the fourth H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the fifth H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the sixth H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the seventh H1+ site, H1+ is bonded in a single-bond geometry to one C+0.89+ atom. In the eighth H1+ site, H1+ is bonded in a single-bond geometry to one C+0.89+ atom. In the ninth H1+ site, H1+ is bonded in a single-bond geometry to one C+0.89+ atom. In the tenth H1+ site, H1+ is bonded in a single-bond geometry to one C+0.89+ atom. In the eleventh H1+ site, H1+ is bonded in a single-bond geometry to one C+0.89+ atom. In the twelfth H1+ site, H1+ is bonded in a single-bond geometry to one C+0.89+ atom. In the thirteenth H1+ site, H1+ is bonded in a single-bond geometry to one C+0.89+ atom. In the fourteenth H1+ site, H1+ is bonded in a single-bond geometry to one C+0.89+ atom. In the fifteenth H1+ site, H1+ is bonded in a single-bond geometry to one C+0.89+ atom. In the sixteenth H1+ site, H1+ is bonded in a single-bond geometry to one C+0.89+ atom. In the seventeenth H1+ site, H1+ is bonded in a single-bond geometry to one C+0.89+ atom. In the eighteenth H1+ site, H1+ is bonded in a single-bond geometry to one C+0.89+ atom. In the nineteenth H1+ site, H1+ is bonded in a single-bond geometry to one C+0.89+ atom. In the twentieth H1+ site, H1+ is bonded in a single-bond geometry to one C+0.89+ atom. In the twenty-first H1+ site, H1+ is bonded in a single-bond geometry to one C+0.89+ atom. In the twenty-second H1+ site, H1+ is bonded in a single-bond geometry to one C+0.89+ atom. In the twenty-third H1+ site, H1+ is bonded in a single-bond geometry to one C+0.89+ atom. In the twenty-fourth H1+ site, H1+ is bonded in a single-bond geometry to one C+0.89+ atom. There are three inequivalent S2- sites. In the first S2- site, S2- is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ag1+ and one C+0.89+ atom. In the second S2- site, S2- is bonded in a water-like geometry to one Ag1+ and one C+0.89+ atom. In the third S2- site, S2- is bonded in a water-like geometry to one Ag1+ and one C+0.89+ atom. In each ClO4 cluster, there are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a single-bond geometry to one Cl1- atom. The O–Cl bond length is 1.49 Å. In the second O2- site, O2- is bonded in a single-bond geometry to one Cl1- atom. The O–Cl bond length is 1.46 Å. In the third O2- site, O2- is bonded in a single-bond geometry to one Cl1- atom. The O–Cl bond length is 1.46 Å. In the fourth O2- site, O2- is bonded in a single-bond geometry to one Cl1- atom. The O–Cl bond length is 1.46 Å. Cl1- is bonded in a tetrahedral geometry to four O2- atoms.

36 MATERIALS SCIENCE↗