Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Cu(NO)3”

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.

At least 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Methanol Partial Oxidation on Cu(111) and PtCu(111) Single-Atom Alloy Surfaces: Effect of Surface Oxygen Coverage on Selectivity

The selective oxidation of methanol to formaldehyde on Cu surfaces is an important and well-studied reaction. However, a systematic analysis of product selectivity as a function of oxygen coverage on Cu(111) and Cu-based single-atom alloys (SAAs) has not been previously reported. In this work, we present a comprehensive investigation of deuterated methanol (CD 3 OH) partial oxidation on Cu(111) and 1% PtCu(111) SAA surfaces as a function of preadsorbed oxygen coverage. Temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS) reveal that isolated Pt atoms inhibit the initial surface oxidation of Cu(111) under low oxygen exposures. Despite this difference in oxidation kinetics, the product selectivity remains largely unaffected: on both Cu(111) and PtCu(111), formaldehyde (CD 2 O) is the predominant partial oxidation product over a broad range of oxygen coverages. The selectivity toward formaldehyde peaks at intermediate oxygen coverages (∼0.3 monolayers, ML), indicating the existence of an optimal oxygen loading for partial oxidation. Notably, the similar product selectivities on Cu(111) and PtCu(111) over a range of surface oxygen coverage indicate that Pt single atoms do not significantly alter the reaction pathway or shift the optimal oxygen coverage for formaldehyde formation. Control experiments confirm that Cu(111) is unreactive toward methanol in the absence of oxygen, while PtCu(111) surfaces produce a small amount of formaldehyde even when oxygen is not preadsorbed, indicating that isolated Pt atoms facilitate O−H activation at below 150 K, leading to H 2 desorption, followed by C−D activation at higher temperatures (∼350 K). Density functional theory (DFT)-based calculations show that Pt atoms increase the O 2 dissociation barrier relative to Cu(111), consistent with the observed inhibition of oxidation at low exposures. Overall, this work provides the first detailed selectivity map for methanol oxidation on oxidized Cu(111) and PtCu(111) SAA surfaces. By linking classical mechanistic insights such as methoxy- and formate-mediated pathways with single-atom alloy catalyst design, this work demonstrates that while Pt substitution modulates the oxidation kinetics and oxygen binding, the overall selectivity toward formaldehyde is governed primarily by oxygen coverage. These findings underscore the potential of isolated dopants to tune surface oxidation behavior without compromising the intrinsic partial oxidation selectivity of copper-based catalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Sr4La13Cu17O35F16 by Materials Project

Sr4La13Cu17O35F16 is (Cubic) Perovskite-derived structured and crystallizes in the orthorhombic Pmm2 space group. The structure is three-dimensional. there are four inequivalent Sr sites. In the first Sr site, Sr is bonded to eight O and four F atoms to form SrO8F4 cuboctahedra that share corners with twelve SrO8F4 cuboctahedra, faces with six SrO8F4 cuboctahedra, and faces with eight CuO4F2 octahedra. There are a spread of Sr–O bond distances ranging from 2.77–2.79 Å. There are two shorter (2.77 Å) and two longer (2.79 Å) Sr–F bond lengths. In the second Sr site, Sr is bonded to ten O and two equivalent F atoms to form SrO10F2 cuboctahedra that share corners with eight SrO8F4 cuboctahedra, faces with five SrO8F4 cuboctahedra, and faces with eight CuO6 octahedra. There are a spread of Sr–O bond distances ranging from 2.72–2.92 Å. Both Sr–F bond lengths are 2.71 Å. In the third Sr site, Sr is bonded to eight O and four F atoms to form distorted SrO8F4 cuboctahedra that share corners with four equivalent LaO8F4 cuboctahedra, corners with eight SrO8F4 cuboctahedra, a faceface with one LaO8F4 cuboctahedra, faces with five SrO8F4 cuboctahedra, and faces with eight CuO4F2 octahedra. There are a spread of Sr–O bond distances ranging from 2.63–3.08 Å. There are two shorter (2.62 Å) and two longer (3.02 Å) Sr–F bond lengths. In the fourth Sr site, Sr is bonded to eight O and four F atoms to form SrO8F4 cuboctahedra that share corners with twelve SrO8F4 cuboctahedra, faces with six SrO8F4 cuboctahedra, and faces with eight CuO4F2 octahedra. There are a spread of Sr–O bond distances ranging from 2.73–2.83 Å. There are two shorter (2.74 Å) and two longer (2.82 Å) Sr–F bond lengths. There are thirteen inequivalent La sites. In the first La site, La is bonded to eight O and four F atoms to form distorted LaO8F4 cuboctahedra that share corners with four equivalent SrO8F4 cuboctahedra, corners with eight LaO8F4 cuboctahedra, a faceface with one SrO8F4 cuboctahedra, faces with five LaO8F4 cuboctahedra, and faces with eight CuO4F2 octahedra. There are a spread of La–O bond distances ranging from 2.52–3.00 Å. There are two shorter (2.56 Å) and two longer (2.95 Å) La–F bond lengths. In the second La site, La is bonded to eight O and four F atoms to form LaO8F4 cuboctahedra that share corners with twelve LaO8F4 cuboctahedra, faces with six LaO8F4 cuboctahedra, and faces with eight CuO4F2 octahedra. There are a spread of La–O bond distances ranging from 2.71–2.84 Å. There are two shorter (2.72 Å) and two longer (2.82 Å) La–F bond lengths. In the third La site, La is bonded to eight O and four F atoms to form LaO8F4 cuboctahedra that share corners with twelve LaO8F4 cuboctahedra, faces with six LaO8F4 cuboctahedra, and faces with eight CuO4F2 octahedra. There are a spread of La–O bond distances ranging from 2.63–2.90 Å. There are two shorter (2.65 Å) and two longer (2.88 Å) La–F bond lengths. In the fourth La site, La is bonded to eight O and four F atoms to form LaO8F4 cuboctahedra that share corners with twelve LaO8F4 cuboctahedra, faces with six LaO8F4 cuboctahedra, and faces with eight CuO4F2 octahedra. There are a spread of La–O bond distances ranging from 2.77–2.79 Å. There are two shorter (2.77 Å) and two longer (2.78 Å) La–F bond lengths. In the fifth La site, La is bonded to eight O and four F atoms to form LaO8F4 cuboctahedra that share corners with twelve LaO8F4 cuboctahedra, faces with six LaO8F4 cuboctahedra, and faces with eight CuO4F2 octahedra. There are a spread of La–O bond distances ranging from 2.75–2.81 Å. There are two shorter (2.75 Å) and two longer (2.80 Å) La–F bond lengths. In the sixth La site, La is bonded to eight O and four F atoms to form LaO8F4 cuboctahedra that share corners with twelve LaO8F4 cuboctahedra, faces with six LaO8F4 cuboctahedra, and faces with eight CuO4F2 octahedra. All La–O bond lengths are 2.78 Å. There are two shorter (2.77 Å) and two longer (2.78 Å) La–F bond lengths. In the seventh La site, La is bonded to eight O and four F atoms to form LaO8F4 cuboctahedra that share corners with twelve LaO8F4 cuboctahedra, faces with six LaO8F4 cuboctahedra, and faces with eight CuO4F2 octahedra. All La–O bond lengths are 2.78 Å. There are two shorter (2.77 Å) and two longer (2.78 Å) La–F bond lengths. In the eighth La site, La is bonded to eight O and four F atoms to form LaO8F4 cuboctahedra that share corners with twelve LaO8F4 cuboctahedra, faces with six LaO8F4 cuboctahedra, and faces with eight CuO4F2 octahedra. There are a spread of La–O bond distances ranging from 2.76–2.80 Å. There are two shorter (2.75 Å) and two longer (2.79 Å) La–F bond lengths. In the ninth La site, La is bonded to eight O and four F atoms to form LaO8F4 cuboctahedra that share corners with twelve LaO8F4 cuboctahedra, faces with six LaO8F4 cuboctahedra, and faces with eight CuO4F2 octahedra. There are a spread of La–O bond distances ranging from 2.77–2.79 Å. There are two shorter (2.77 Å) and two longer (2.78 Å) La–F bond lengths. In the tenth La site, La is bonded to eight O and four F atoms to form LaO8F4 cuboctahedra that share corners with twelve LaO8F4 cuboctahedra, faces with six LaO8F4 cuboctahedra, and faces with eight CuO4F2 octahedra. There are a spread of La–O bond distances ranging from 2.65–2.88 Å. There are two shorter (2.67 Å) and two longer (2.86 Å) La–F bond lengths. In the eleventh La site, La is bonded to eight O and four F atoms to form LaO8F4 cuboctahedra that share corners with twelve LaO8F4 cuboctahedra, faces with six LaO8F4 cuboctahedra, and faces with eight CuO4F2 octahedra. There are a spread of La–O bond distances ranging from 2.72–2.83 Å. There are two shorter (2.73 Å) and two longer (2.82 Å) La–F bond lengths. In the twelfth La site, La is bonded to eight O and four F atoms to form distorted LaO8F4 cuboctahedra that share corners with eight LaO8F4 cuboctahedra, faces with five LaO8F4 cuboctahedra, and faces with eight CuO4F2 octahedra. There are a spread of La–O bond distances ranging from 2.55–2.98 Å. There are two shorter (2.58 Å) and two longer (2.94 Å) La–F bond lengths. In the thirteenth La site, La is bonded in a 12-coordinate geometry to ten O and two equivalent F atoms. There are a spread of La–O bond distances ranging from 2.47–3.16 Å. Both La–F bond lengths are 3.12 Å. There are seventeen inequivalent Cu sites. In the first Cu site, Cu is bonded to six O atoms to form CuO6 octahedra that share corners with six CuO6 octahedra and faces with four equivalent SrO10F2 cuboctahedra. The corner-sharing octahedra tilt angles range from 0–10°. There are a spread of Cu–O bond distances ranging from 1.93–2.04 Å. In the second Cu site, Cu is bonded to four O and two equivalent F atoms to form CuO4F2 octahedra that share corners with six CuO4F2 octahedra and faces with eight LaO8F4 cuboctahedra. The corner-sharing octahedra tilt angles range from 0–6°. There are a spread of Cu–O bond distances ranging from 1.94–1.98 Å. Both Cu–F bond lengths are 1.97 Å. In the third Cu site, Cu is bonded to four O and two equivalent F atoms to form CuO4F2 octahedra that share corners with six CuO6 octahedra and faces with eight SrO8F4 cuboctahedra. The corner-sharing octahedra tilt angles range from 0–1°. There are a spread of Cu–O bond distances ranging from 1.94–1.96 Å. Both Cu–F bond lengths are 1.97 Å. In the fourth Cu site, Cu is bonded to four O and two equivalent F atoms to form CuO4F2 octahedra that share corners with six CuO4F2 octahedra and faces with eight SrO8F4 cuboctahedra. The corner-sharing octahedral tilt angles are 0°. There are a spread of Cu–O bond distances ranging from 1.95–1.97 Å. Both Cu–F bond lengths are 1.96 Å. In the fifth Cu site, Cu is bonded to four O and two equivalent F atoms to form CuO4F2 octahedra that share corners with six CuO4F2 octahedra and faces with eight SrO8F4 cuboctahedra. The corner-sharing octahedra tilt angles range from 0–3°. There are a spread of Cu–O bond distances ranging from 1.93–1.99 Å. Both Cu–F bond lengths are 1.97 Å. In the sixth Cu site, Cu is bonded to four O and two equivalent F atoms to form CuO4F2 octahedra that share corners with six CuO4F2 octahedra, faces with four equivalent SrO8F4 cuboctahedra, and faces with four equivalent LaO8F4 cuboctahedra. The corner-sharing octahedra tilt angles range from 0–16°. There are a spread of Cu–O bond distances ranging from 1.90–2.02 Å. Both Cu–F bond lengths are 1.98 Å. In the seventh Cu site, Cu is bonded to four O and two equivalent F atoms to form CuO4F2 octahedra that share corners with six CuO4F2 octahedra and faces with eight LaO8F4 cuboctahedra. The corner-sharing octahedra tilt angles range from 0–8°. There are a spread of Cu–O bond distances ranging from 1.94–1.99 Å. Both Cu–F bond lengths are 1.97 Å. In the eighth Cu site, Cu is bonded to four O and two equivalent F atoms to form CuO4F2 octahedra that share corners with six CuO4F2 octahedra and faces with eight LaO8F4 cuboctahedra. The corner-sharing octahedra tilt angles range from 0–4°. There are a spread of Cu–O bond distances ranging from 1.94–1.97 Å. Both Cu–F bond lengths are 1.97 Å. In the ninth Cu site, Cu is bonded to four O and two equivalent F atoms to form CuO4F2 octahedra that share corners with six CuO4F2 octahedra and faces with eight LaO8F4 cuboctahedra. The corner-sharing octahedra tilt angles range from 0–2°. There is three shorter (1.96 Å) and one longer (1.97 Å) Cu–O bond length. Both Cu–F bond lengths are 1.97 Å. In the tenth Cu site, Cu is bonded to four O and two equivalent F atoms to form CuO4F2 octahedra that share corners with six CuO4F2 octahedra and faces with eight LaO8F4 cuboctahedra. The corner-sharing octahedra tilt angles range from 0–1°. All Cu–O bond lengths are 1.96 Å. Both Cu–F bond lengths are 1.97 Å. In the eleventh Cu site, Cu is bonded to four O and two equivalent F atoms to form CuO4F2 octahedra that share corners with six CuO4F2 octahedra and faces with eight LaO8F4 cuboctahedra. The corner-sharing octahedral tilt angles are 0°. All Cu–O bond lengths are 1.96 Å. Both Cu–F bond lengths are 1.97 Å. In the twelfth Cu site, Cu is bonded to four O and two equivalent F atoms to form CuO4F2 octahedra that share corners with six CuO4F2 octahedra and faces with eight LaO8F4 cuboctahedra. The corner-sharing octahedral tilt angles are 0°. All Cu–O bond lengths are 1.96 Å. Both Cu–F bond lengths are 1.97 Å. In the thirteenth Cu site, Cu is bonded to four O and two equivalent F atoms to form CuO4F2 octahedra that share corners with six CuO4F2 octahedra and faces with eight LaO8F4 cuboctahedra. The corner-sharing octahedral tilt angles are 0°. All Cu–O bond lengths are 1.96 Å. Both Cu–F bond lengths are 1.97 Å. In the fourteenth Cu site, Cu is bonded to four O and two equivalent F atoms to form CuO4F2 octahedra that share corners with six CuO4F2 octahedra and faces with eight LaO8F4 cuboctahedra. The corner-sharing octahedra tilt angles range from 0–1°. All Cu–O bond lengths are 1.96 Å. Both Cu–F bond lengths are 1.97 Å. In the fifteenth Cu site, Cu is bonded to four O and two equivalent F atoms to form CuO4F2 octahedra that share corners with six CuO4F2 octahedra and faces with eight LaO8F4 cuboctahedra. The corner-sharing octahedra tilt angles range from 0–1°. There is three shorter (1.96 Å) and one longer (1.97 Å) Cu–O bond length. Both Cu–F bond lengths are 1.97 Å. In the sixteenth Cu site, Cu is bonded to four O and two equivalent F atoms to form CuO4F2 octahedra that share corners with six CuO4F2 octahedra and faces with eight LaO8F4 cuboctahedra. The corner-sharing octahedra tilt angles range from 0–3°. There are a spread of Cu–O bond distances ranging from 1.95–1.97 Å. Both Cu–F bond lengths are 1.97 Å. In the seventeenth Cu site, Cu is bonded to four O and two equivalent F atoms to form CuO4F2 octahedra that share corners with six CuO6 octahedra and faces with four equivalent LaO8F4 cuboctahedra. The corner-sharing octahedra tilt angles range from 0–12°. There are

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Li2Cu3F9 by Materials Project

Li2Cu3F9 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. there are two inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to five F1- atoms to form distorted LiF5 square pyramids that share corners with two equivalent CuF6 octahedra, an edgeedge with one CuF6 octahedra, and an edgeedge with one LiF5 square pyramid. The corner-sharing octahedra tilt angles range from 15–26°. There are a spread of Li–F bond distances ranging from 1.97–2.24 Å. In the second Li1+ site, Li1+ is bonded in a 4-coordinate geometry to four F1- atoms. There are a spread of Li–F bond distances ranging from 1.87–2.02 Å. There are three inequivalent Cu+2.33+ sites. In the first Cu+2.33+ site, Cu+2.33+ is bonded to six F1- atoms to form distorted CuF6 octahedra that share corners with two equivalent CuF6 octahedra, corners with two equivalent LiF5 square pyramids, an edgeedge with one CuF6 octahedra, and an edgeedge with one LiF5 square pyramid. The corner-sharing octahedra tilt angles range from 44–55°. There are a spread of Cu–F bond distances ranging from 1.86–2.38 Å. In the second Cu+2.33+ site, Cu+2.33+ is bonded to six F1- atoms to form a mixture of edge and corner-sharing CuF6 octahedra. The corner-sharing octahedra tilt angles range from 44–55°. There are a spread of Cu–F bond distances ranging from 1.94–2.14 Å. In the third Cu+2.33+ site, Cu+2.33+ is bonded in a distorted rectangular see-saw-like geometry to five F1- atoms. There are a spread of Cu–F bond distances ranging from 1.82–2.57 Å. There are nine inequivalent F1- sites. In the first F1- site, F1- is bonded in a T-shaped geometry to two Li1+ and one Cu+2.33+ atom. In the second F1- site, F1- is bonded in a rectangular see-saw-like geometry to three Li1+ and one Cu+2.33+ atom. In the third F1- site, F1- is bonded in a 3-coordinate geometry to one Li1+ and two equivalent Cu+2.33+ atoms. In the fourth F1- site, F1- is bonded in a water-like geometry to two equivalent Cu+2.33+ atoms. In the fifth F1- site, F1- is bonded in a distorted trigonal planar geometry to three Cu+2.33+ atoms. In the sixth F1- site, F1- is bonded in a 2-coordinate geometry to one Li1+ and two Cu+2.33+ atoms. In the seventh F1- site, F1- is bonded in a 3-coordinate geometry to two Li1+ and one Cu+2.33+ atom. In the eighth F1- site, F1- is bonded in a 2-coordinate geometry to three Cu+2.33+ atoms. In the ninth F1- site, F1- is bonded in a bent 150 degrees geometry to two Cu+2.33+ atoms.

36 MATERIALS SCIENCE↗
NASA NTRS1986

The nature of the bonding in XCO for X = Fe, Ni, and Cu

The bonding in the (5,3)Sigma - and 3Delta states of FeCO, the (3,1)Sigma + , 3Delta, and 3Pi states of NiCO, and the 2Sigma + state of CuCO are analyzed using the constrained-space orbital-variation (CSOV) technique for both (CASSCF) and SCF wave functions. The bonding is discussed in terms of sigma repulsion between the metals 4s and the CO 5-sigma and CO-to-metal sigma donation when there is an empty or partly occupied d-sigma orbital and metal-to-CO 2pi(asterisk) backdonation. The bonding is compared for the different metals and between the different states.

Bauschlicher, C. W., Jr.↗
DOE OSTI2020

Ambient and High Pressure CuNiSb 2 : Metal-Ordered and Metal-Disordered NiAs-Type Derivative Pnictides

The mineral Zlatogorite, CuNiSb 2 , was synthesized in the laboratory for the first time by annealing elements at ambient pressure (CuNiSb 2 -AP). Rietveld refinement of synchrotron powder X-ray diffraction data indicates that CuNiSb 2 -AP crystallizes in the NiAs-derived structure ( P 3 m 1, #164) with Cu and Ni ordering. The structure consists of alternate NiSb 6 and CuSb 6 octahedral layers via face-sharing. The formation of such structure instead of metal disordered NiAs-type structure ( P 6 3 / mm c, #194) is validated by the lower energy of the ordered phase by first-principle calculations. Interatomic crystal orbital Hamilton population, electron localization function, and charge density analysis reveal strong Ni-Sb, Cu-Sb, and Cu-Ni bonding and long weak Sb-Sb interactions in CuNiSb 2 -AP. The magnetic measurement indicates that CuNiSb 2 -AP is Pauli paramagnetic. First-principle calculations and experimental electrical resistivity measurements reveal that CuNiSb 2 -AP is a metal. The low Seebeck coefficient and large thermal conductivity suggest that CuNiSb 2 is not a potential thermoelectric material. Single crystals were grown by chemical vapor transport. The high pressure sample (CuNiSb 2 -8 GPa) was prepared by pressing CuNiSb 2 -AP at 700 °C and 8 GPa. However, the structures of single crystal and CuNiSb 2 -8 GPa are best fit with a disordered metal structure in the P 3 m 1 space group, corroborated by transmission electron microscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1980

Determination of the thermal rate coefficient, products, and branching ratios for the reaction of O/+/ /D-2/ with N2

Atmosphere Explorer-C satellite measurements are used to determine rate coefficients (RCs) for the following reactions: O(+)(D-2) + N2 yields N2(+) + O (reaction 1), O(+)(D-2) + N2 yields O(+)(S-4) + N2 (reaction 2), and O(+)(D-2) + N2 yields NO(+) + N (reaction 3). Results show the RC for reaction 1 to be 1 (plus 1 or minus 0.5) x 10 to the -10th cu cm per sec, for reaction 2 to be 3 (plus 1 or minus 2) x 10 to the -11th cu cm per sec, and 3 to be less than 5.5 x 10 to the -11th cu cm per sec. It is also found that the reaction of O(+)(D-2) with N2 does not constitute a detectable source of NO(+) ions in the thermosphere.

Torr, D. G.↗
DOE OSTI2024

Composition-Dependent Reconstructions of Titanium Oxide Clusters and Cu(111) Support via Cluster-Adatom Interactions

Mass-selected cluster deposition and scanning tunneling microscopy (STM) were used to investigate the surface structure and thermal stability of Ti 3 O y (y = 5, 6) clusters on a Cu(111) surface. STM imaging shows that the substoichiometric Ti 3 O 5 clusters aggregate into large dendritic assemblies at step edges, while the stoichiometric Ti 3 O 6 clusters are highly dispersed as single or small groupings of clusters. Cluster deposition also results in extensive reconstruction of the Cu(111) surface. The Ti 3 O 5 /Cu(111) surface exhibits one Cu-layer deep pits that are ringed by cluster assemblies that nucleate and grow at the perimeter step edges. By comparison, the Ti 3 O 6 /Cu(111) surface consists of irregular step edges and small one Cu-layer islands that are decorated with clusters. The restructuring of the Cu(111) surface is attributed to strong Cu-cluster interactions that release Cu adatoms from the step edges. This mechanism is supported by density functional theory (DFT) calculations, which predict that the Cu adatom attachment to the clusters is energetically favorable. Annealing the surfaces at elevated temperatures (400-700 K) results in higher densities of irregular steps, pits and isolated Cu islands as well as increased cluster aggregation. In conclusion, this work highlights adatom-cluster interactions as another manifestation of strong cluster-support interactions that can significantly alter the nature of the oxide-metal interface.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Exploring Spin‐Orbit Effects in a [Cu 6 Tl] + Nanocluster Featuring an Uncommon Tl−H Interaction

Reaction of [CuH(PPh 3 )] 6 with 1 equiv. of Tl(OTf) results in formation of [Cu 6 TlH 6 (PPh 3 ) 6 ][OTf] ([1]OTf]), which can be isolated in good yields. Variable-temperature 1 H NMR spectroscopy, in combination with density functional theory (DFT) calculations, confirms the presence of a rare Tl−H orbital interaction. According to DFT, the 1 H chemical shift of the Tl-adjacent hydride ligands of [1] + includes 7.7 ppm of deshielding due to spin-orbit effects from the heavy Tl atom. In conclusion, this study provides valuable new insights into a rare class of metal hydrides, given that [1][OTf] is only the third isolable species reported to contain a Tl−H interaction.

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

Dynamic Boundary Layer Simulation of Pulsed CO 2 Electrolysis on a Copper Catalyst

Pulsed electrolysis has been demonstrated to improve the faradaic efficiency (FE) to C 2+ products during the electrochemical reduction of CO 2 over a Cu catalyst, but the nature of this enhancement is poorly understood. Herein, we developed a time-dependent continuum model of pulsed CO 2 electrolysis on Cu in 0.1 M CsHCO 3 that faithfully represents the experimentally observed effects of pulsed electrolysis. This work shows that pulsing results in dynamic changes in the pH and CO 2 concentration near the Cu surface, which lead to an enhanced C 2+ FE as a consequence of repeatedly accessing a transient state of heightened pH and CO 2 concentration at high cathodic overpotential. Using these insights, a variety of pulse shapes were explored to establish operating conditions that maximize the rate of C 2+ product formation and minimize the rates of H 2 and C 1 product formation.

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

Materials Data on Cd5Cu2 by Materials Project

Cu2Cd5 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. there are two inequivalent Cu sites. In the first Cu site, Cu is bonded to two equivalent Cu and ten Cd atoms to form distorted CuCd10Cu2 cuboctahedra that share corners with four equivalent CuCd10Cu2 cuboctahedra, faces with two equivalent CdCd6Cu6 cuboctahedra, and faces with six equivalent CuCd10Cu2 cuboctahedra. Both Cu–Cu bond lengths are 2.78 Å. There are a spread of Cu–Cd bond distances ranging from 2.73–3.14 Å. In the second Cu site, Cu is bonded in a 9-coordinate geometry to nine Cd atoms. There are six shorter (2.63 Å) and three longer (2.95 Å) Cu–Cd bond lengths. There are three inequivalent Cd sites. In the first Cd site, Cd is bonded in a 1-coordinate geometry to four Cu and nine Cd atoms. There are a spread of Cd–Cd bond distances ranging from 2.96–3.25 Å. In the second Cd site, Cd is bonded in a 3-coordinate geometry to three Cu and eight equivalent Cd atoms. In the third Cd site, Cd is bonded to six equivalent Cu and six equivalent Cd atoms to form distorted CdCd6Cu6 cuboctahedra that share faces with two equivalent CdCd6Cu6 cuboctahedra and faces with six equivalent CuCd10Cu2 cuboctahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2023

MXene Nanosheets Functionalized with Cu Atoms for Urea Adsorption in Aqueous Media

Ti 3 C 2 T x MXene is an emerging family of two-dimensional materials, and because of its large specific surface area, it has potential for many applications. Herein, a new application using Cu-doped MILD (minimally intensive layer delamination) synthesized Ti 3 C 2 T x MXene for urea removal is demonstrated. The doping of Cu on MXene results in an increase in its affinity for urea adsorption as compared to the pristine MILD synthesized MXene due to the formation of the Cu–urea complex. Previous computational studies have shown that the adsorption energies of urea on the MXene surface can be improved in the presence of Cu. The valence state of Cu in the doped MILD synthesized MXene, which binds on to the surface via Ti–O–Cu linkage, is between 0 and +1 as verified by XAS and XPS. As the optimal urea adsorption occurs on Cu as a single atom site, an increase in Cu doping on MXene does not increase urea removal due to Cu agglomeration. Furthermore, looking at the adsorption behaviour, it seems that Cu-doped MXene follows the monolayer adsorption on homogenous surface model.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Rb2Gd4Cu4S9 by Materials Project

Rb2Gd4Cu4S9 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are two inequivalent Rb1+ sites. In the first Rb1+ site, Rb1+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Rb–S bond distances ranging from 3.25–3.86 Å. In the second Rb1+ site, Rb1+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Rb–S bond distances ranging from 3.25–3.90 Å. There are four inequivalent Gd3+ sites. In the first Gd3+ site, Gd3+ is bonded to six S2- atoms to form GdS6 octahedra that share corners with three GdS6 octahedra, a cornercorner with one CuS4 tetrahedra, edges with five GdS6 octahedra, and edges with two equivalent CuS4 tetrahedra. The corner-sharing octahedra tilt angles range from 1–31°. There are a spread of Gd–S bond distances ranging from 2.72–2.86 Å. In the second Gd3+ site, Gd3+ is bonded to six S2- atoms to form GdS6 octahedra that share a cornercorner with one GdS6 octahedra, corners with four equivalent CuS4 tetrahedra, edges with four GdS6 octahedra, and edges with five CuS4 tetrahedra. The corner-sharing octahedral tilt angles are 31°. There are a spread of Gd–S bond distances ranging from 2.72–2.86 Å. In the third Gd3+ site, Gd3+ is bonded to six S2- atoms to form GdS6 octahedra that share a cornercorner with one GdS6 octahedra, corners with four equivalent CuS4 tetrahedra, edges with four GdS6 octahedra, and edges with five CuS4 tetrahedra. The corner-sharing octahedral tilt angles are 30°. There are a spread of Gd–S bond distances ranging from 2.72–2.85 Å. In the fourth Gd3+ site, Gd3+ is bonded to six S2- atoms to form GdS6 octahedra that share corners with three GdS6 octahedra, a cornercorner with one CuS4 tetrahedra, edges with five GdS6 octahedra, and edges with two equivalent CuS4 tetrahedra. The corner-sharing octahedra tilt angles range from 1–30°. There are a spread of Gd–S bond distances ranging from 2.72–2.86 Å. There are four inequivalent Cu1+ sites. In the first Cu1+ site, Cu1+ is bonded to four S2- atoms to form CuS4 tetrahedra that share corners with four equivalent GdS6 octahedra, corners with four CuS4 tetrahedra, edges with three GdS6 octahedra, and an edgeedge with one CuS4 tetrahedra. The corner-sharing octahedra tilt angles range from 14–60°. There are a spread of Cu–S bond distances ranging from 2.37–2.53 Å. In the second Cu1+ site, Cu1+ is bonded to four S2- atoms to form CuS4 tetrahedra that share a cornercorner with one GdS6 octahedra, corners with four CuS4 tetrahedra, and edges with four GdS6 octahedra. The corner-sharing octahedral tilt angles are 3°. There are a spread of Cu–S bond distances ranging from 2.33–2.59 Å. In the third Cu1+ site, Cu1+ is bonded to four S2- atoms to form CuS4 tetrahedra that share a cornercorner with one GdS6 octahedra, corners with four CuS4 tetrahedra, and edges with four GdS6 octahedra. The corner-sharing octahedral tilt angles are 3°. There are a spread of Cu–S bond distances ranging from 2.34–2.59 Å. In the fourth Cu1+ site, Cu1+ is bonded to four S2- atoms to form CuS4 tetrahedra that share corners with four equivalent GdS6 octahedra, corners with four CuS4 tetrahedra, edges with three GdS6 octahedra, and an edgeedge with one CuS4 tetrahedra. The corner-sharing octahedra tilt angles range from 15–59°. There are a spread of Cu–S bond distances ranging from 2.35–2.59 Å. There are nine inequivalent S2- sites. In the first S2- site, S2- is bonded in a 7-coordinate geometry to two equivalent Rb1+, two equivalent Gd3+, and three Cu1+ atoms. In the second S2- site, S2- is bonded in a 7-coordinate geometry to two equivalent Rb1+, two equivalent Gd3+, and three Cu1+ atoms. In the third S2- site, S2- is bonded to two equivalent Rb1+, three Gd3+, and one Cu1+ atom to form distorted SRb2Gd3Cu octahedra that share corners with two equivalent SRbGd3Cu2 octahedra and edges with four SRb2Gd3Cu octahedra. The corner-sharing octahedra tilt angles range from 40–41°. In the fourth S2- site, S2- is bonded to two equivalent Rb1+, three Gd3+, and one Cu1+ atom to form distorted SRb2Gd3Cu octahedra that share corners with two equivalent SRbGd3Cu2 octahedra and edges with four SRb2Gd3Cu octahedra. The corner-sharing octahedra tilt angles range from 40–42°. In the fifth S2- site, S2- is bonded in a 6-coordinate geometry to two equivalent Rb1+, two Gd3+, and two equivalent Cu1+ atoms. In the sixth S2- site, S2- is bonded in a 6-coordinate geometry to two equivalent Rb1+, two Gd3+, and two equivalent Cu1+ atoms. In the seventh S2- site, S2- is bonded in a distorted square co-planar geometry to two Rb1+ and four Gd3+ atoms. In the eighth S2- site, S2- is bonded to one Rb1+, three Gd3+, and two equivalent Cu1+ atoms to form distorted SRbGd3Cu2 octahedra that share corners with two equivalent SRb2Gd3Cu octahedra and edges with four SRbGd3Cu2 octahedra. The corner-sharing octahedra tilt angles range from 40–41°. In the ninth S2- site, S2- is bonded to one Rb1+, three Gd3+, and two equivalent Cu1+ atoms to form distorted SRbGd3Cu2 octahedra that share corners with two equivalent SRb2Gd3Cu octahedra and edges with four SRbGd3Cu2 octahedra. The corner-sharing octahedra tilt angles range from 40–42°.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Establishing the Role of Operating Potential and Mass Transfer in Multicarbon Product Generation for Photoelectrochemical CO 2 Reduction Cells Using a Cu Catalyst

There is increasing interest in the possibility of photoelectrochemical (PEC) reduction of CO 2 to C 2+ products; however, the criteria for maximizing PEC solar-to-C 2+ (STC 2+ ) rates are not well understood. We report here a continuum-scale model of PEC CO 2 reduction (CO 2 R) on Cu in 0.1 M CsHCO 3 and use it to optimize the design and operating conditions for generating C 2+ products. Furthermore, we demonstrate that the potential-dependent product distribution of CO 2 R on Cu requires operating near the potential that maximizes C 2+ generation rates ($V$ id ), unlike PEC water splitting, which desires operation at the maximum photocurrent density. Because of this requirement, the criterion for a high STC 2+ rate includes high-photocurrent semiconductors with photovoltages near $V$ id and low series resistance. The STC 2+ rate in these systems is enhanced by optimal CO 2 transport and exhibits low sensitivity to dirunal solar irradiance variations.

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

Materials Data on CaUCu(PO7)2 by Materials Project

CaUCu(PO7)2 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are three inequivalent Ca sites. In the first Ca site, Ca is bonded in a 8-coordinate geometry to eight O atoms. There are a spread of Ca–O bond distances ranging from 2.35–2.65 Å. In the second Ca site, Ca is bonded in a 8-coordinate geometry to eight O atoms. There are a spread of Ca–O bond distances ranging from 2.35–2.66 Å. In the third Ca site, Ca is bonded in a 8-coordinate geometry to eight O atoms. There are a spread of Ca–O bond distances ranging from 2.35–2.65 Å. There are three inequivalent U sites. In the first U site, U is bonded to seven O atoms to form distorted UO7 pentagonal bipyramids that share corners with three PO4 tetrahedra and an edgeedge with one PO4 tetrahedra. There are a spread of U–O bond distances ranging from 1.81–2.49 Å. In the second U site, U is bonded to seven O atoms to form distorted UO7 pentagonal bipyramids that share corners with three PO4 tetrahedra and an edgeedge with one PO4 tetrahedra. There are a spread of U–O bond distances ranging from 1.81–2.49 Å. In the third U site, U is bonded to seven O atoms to form distorted UO7 pentagonal bipyramids that share corners with three PO4 tetrahedra and an edgeedge with one PO4 tetrahedra. There are a spread of U–O bond distances ranging from 1.81–2.49 Å. There are four inequivalent Cu sites. In the first Cu site, Cu is bonded to six O atoms to form distorted CuO6 octahedra that share corners with two PO4 tetrahedra. There are a spread of Cu–O bond distances ranging from 1.78–2.43 Å. In the second Cu site, Cu is bonded to six O atoms to form distorted CuO6 octahedra that share corners with two PO4 tetrahedra. There are a spread of Cu–O bond distances ranging from 1.78–2.43 Å. In the third Cu site, Cu is bonded in a distorted square co-planar geometry to four O atoms. There is two shorter (1.76 Å) and two longer (1.87 Å) Cu–O bond length. In the fourth Cu site, Cu is bonded in a distorted square co-planar geometry to four O atoms. There is two shorter (1.76 Å) and two longer (1.87 Å) Cu–O bond length. There are seven inequivalent P sites. In the first P site, P is bonded to four O atoms to form PO4 tetrahedra that share a cornercorner with one CuO6 octahedra and an edgeedge with one UO7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 44°. There are a spread of P–O bond distances ranging from 1.53–1.60 Å. In the second P site, P is bonded to four O atoms to form PO4 tetrahedra that share a cornercorner with one CuO6 octahedra and an edgeedge with one UO7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 44°. There are a spread of P–O bond distances ranging from 1.53–1.60 Å. In the third P site, P is bonded to four O atoms to form PO4 tetrahedra that share a cornercorner with one CuO6 octahedra and an edgeedge with one UO7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 44°. There are a spread of P–O bond distances ranging from 1.53–1.60 Å. In the fourth P site, P is bonded to four O atoms to form PO4 tetrahedra that share corners with three UO7 pentagonal bipyramids. There are a spread of P–O bond distances ranging from 1.53–1.58 Å. In the fifth P site, P is bonded to four O atoms to form PO4 tetrahedra that share corners with three UO7 pentagonal bipyramids. There are a spread of P–O bond distances ranging from 1.53–1.58 Å. In the sixth P site, P is bonded to four O atoms to form PO4 tetrahedra that share corners with three equivalent UO7 pentagonal bipyramids. There are a spread of P–O bond distances ranging from 1.53–1.58 Å. In the seventh P site, P is bonded to four O atoms to form PO4 tetrahedra that share corners with three equivalent UO7 pentagonal bipyramids. There are a spread of P–O bond distances ranging from 1.53–1.58 Å. There are fifty inequivalent O sites. In the first O site, O is bonded in a 1-coordinate geometry to one Ca, one U, and one P atom. In the second O site, O is bonded in a 1-coordinate geometry to one Ca, one U, and one P atom. In the third O site, O is bonded in a 1-coordinate geometry to one Ca, one U, and one P atom. In the fourth O site, O is bonded in a 1-coordinate geometry to one Ca, one U, and one P atom. The O–Ca bond length is 2.35 Å. The O–U bond length is 2.49 Å. The O–P bond length is 1.55 Å. In the fifth O site, O is bonded in a 1-coordinate geometry to one Ca, one U, and one P atom. In the sixth O site, O is bonded in a 1-coordinate geometry to one Ca, one U, and one P atom. In the seventh O site, O is bonded in a 1-coordinate geometry to one Ca, one U, and one P atom. The O–Ca bond length is 2.35 Å. The O–U bond length is 2.49 Å. The O–P bond length is 1.55 Å. In the eighth O site, O is bonded in a 1-coordinate geometry to one Ca, one U, and one P atom. In the ninth O site, O is bonded in a 3-coordinate geometry to one Ca, one Cu, and one P atom. In the tenth O site, O is bonded in a 3-coordinate geometry to one Ca, one Cu, and one P atom. In the eleventh O site, O is bonded in a 3-coordinate geometry to one Ca, one Cu, and one P atom. The O–Ca bond length is 2.50 Å. In the twelfth O site, O is bonded in a 3-coordinate geometry to one Ca, one Cu, and one P atom. The O–P bond length is 1.60 Å. In the thirteenth O site, O is bonded in a water-like geometry to one Ca and one P atom. In the fourteenth O site, O is bonded in a water-like geometry to one Ca and one P atom. In the fifteenth O site, O is bonded in a water-like geometry to one Ca and one P atom. The O–Ca bond length is 2.44 Å. In the sixteenth O site, O is bonded in a water-like geometry to one Ca and one P atom. The O–P bond length is 1.53 Å. In the seventeenth O site, O is bonded in a 1-coordinate geometry to one Ca, one U, and one P atom. In the eighteenth O site, O is bonded in a 1-coordinate geometry to one Ca, one U, and one P atom. In the nineteenth O site, O is bonded in a 1-coordinate geometry to one Ca, one U, and one P atom. The O–Ca bond length is 2.62 Å. The O–U bond length is 2.33 Å. In the twentieth O site, O is bonded in a 1-coordinate geometry to one Ca, one U, and one P atom. In the twenty-first O site, O is bonded in a bent 150 degrees geometry to one U and one P atom. In the twenty-second O site, O is bonded in a bent 150 degrees geometry to one U and one P atom. In the twenty-third O site, O is bonded in a bent 150 degrees geometry to one U and one P atom. In the twenty-fourth O site, O is bonded in a bent 150 degrees geometry to one U and one P atom. The O–U bond length is 2.28 Å. In the twenty-fifth O site, O is bonded in a distorted single-bond geometry to one Ca, one U, and one P atom. In the twenty-sixth O site, O is bonded in a distorted single-bond geometry to one Ca, one U, and one P atom. In the twenty-seventh O site, O is bonded in a distorted single-bond geometry to one Ca, one U, and one P atom. The O–Ca bond length is 2.51 Å. The O–U bond length is 2.39 Å. In the twenty-eighth O site, O is bonded in a distorted single-bond geometry to one Ca, one U, and one P atom. In the twenty-ninth O site, O is bonded in a bent 120 degrees geometry to one Cu and one P atom. In the thirtieth O site, O is bonded in a bent 120 degrees geometry to one Cu and one P atom. In the thirty-first O site, O is bonded in a bent 120 degrees geometry to one Cu and one P atom. In the thirty-second O site, O is bonded in a single-bond geometry to one Cu atom. In the thirty-third O site, O is bonded in a single-bond geometry to one Cu atom. In the thirty-fourth O site, O is bonded in a single-bond geometry to one Cu atom. In the thirty-fifth O site, O is bonded in a single-bond geometry to one Cu atom. In the thirty-sixth O site, O is bonded in a water-like geometry to one Ca and one Cu atom. In the thirty-seventh O site, O is bonded in a water-like geometry to one Ca and one Cu atom. In the thirty-eighth O site, O is bonded in a water-like geometry to one Ca and one Cu atom. In the thirty-ninth O site, O is bonded in a water-like geometry to one Ca and one Cu atom. The O–Ca bond length is 2.65 Å. In the fortieth O site, O is bonded in a single-bond geometry to one Cu atom. In the forty-first O site, O is bonded in a single-bond geometry to one Cu atom. In the forty-second O site, O is bonded in a single-bond geometry to one Cu atom. In the forty-third O site, O is bonded in a distorted single-bond geometry to one U atom. In the forty-fourth O site, O is bonded in a distorted single-bond geometry to one U atom. In the forty-fifth O site, O is bonded in a single-bond geometry to one Ca atom. In the forty-sixth O site, O is bonded in a single-bond geometry to one Ca atom. In the forty-seventh O site, O is bonded in a single-bond geometry to one Ca atom. In the forty-eighth O site, O is bonded in a single-bond geometry to one Ca atom. The O–Ca bond length is 2.55 Å. In the forty-ninth O site, O is bonded in a single-bond geometry to one U atom. In the fiftieth O site, O is bonded in a single-bond geometry to one U atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Na6CuP4(H13O15)2 by Materials Project

Na6CuP4(HO2)14(H2)5H2O2 crystallizes in the triclinic P-1 space group. The structure is three-dimensional and consists of six hydrogen molecules, two water molecules, and one Na6CuP4(HO2)14 framework. In the Na6CuP4(HO2)14 framework, there are three inequivalent Na sites. In the first Na site, Na is bonded in a 4-coordinate geometry to four O atoms. There are a spread of Na–O bond distances ranging from 2.24–2.77 Å. In the second Na site, Na is bonded in a distorted rectangular see-saw-like geometry to four O atoms. There are a spread of Na–O bond distances ranging from 2.17–2.45 Å. In the third Na site, Na is bonded in a 4-coordinate geometry to five O atoms. There are a spread of Na–O bond distances ranging from 2.23–2.92 Å. Cu is bonded in a square co-planar geometry to four O atoms. There is two shorter (1.90 Å) and two longer (2.05 Å) Cu–O bond length. There are two inequivalent P sites. In the first P site, P is bonded to four O atoms to form corner-sharing PO4 tetrahedra. There are a spread of P–O bond distances ranging from 1.48–1.71 Å. In the second P site, P is bonded to four O atoms to form corner-sharing PO4 tetrahedra. There are a spread of P–O bond distances ranging from 1.49–1.66 Å. There are seven inequivalent H sites. In the first H site, H is bonded in a single-bond geometry to one O atom. The H–O bond length is 0.99 Å. In the second H site, H is bonded in a single-bond geometry to one O atom. The H–O bond length is 0.99 Å. In the third H site, H is bonded in a single-bond geometry to one O atom. The H–O bond length is 0.98 Å. In the fourth H site, H is bonded in a single-bond geometry to one O atom. The H–O bond length is 0.99 Å. In the fifth H site, H is bonded in a single-bond geometry to one O atom. The H–O bond length is 1.01 Å. In the sixth H site, H is bonded in a single-bond geometry to one O atom. The H–O bond length is 0.98 Å. In the seventh H site, H is bonded in a single-bond geometry to one O atom. The H–O bond length is 0.97 Å. There are fourteen inequivalent O sites. In the first O site, O is bonded in a distorted bent 150 degrees geometry to two P atoms. In the second O site, O is bonded in a bent 120 degrees geometry to one Cu and one P atom. In the third O site, O is bonded in a distorted single-bond geometry to one P atom. In the fourth O site, O is bonded in a 1-coordinate geometry to one Na, one P, and one O atom. The O–O bond length is 1.39 Å. In the fifth O site, O is bonded in a 3-coordinate geometry to one Cu, one P, and one H atom. In the sixth O site, O is bonded in a 3-coordinate geometry to two Na and one P atom. In the seventh O site, O is bonded in a single-bond geometry to one P atom. In the eighth O site, O is bonded in a distorted bent 120 degrees geometry to one Na and one O atom. The O–O bond length is 1.24 Å. In the ninth O site, O is bonded in a bent 120 degrees geometry to one Na and one O atom. In the tenth O site, O is bonded in a 3-coordinate geometry to two Na and one H atom. In the eleventh O site, O is bonded in a distorted water-like geometry to two equivalent Na and two H atoms. In the twelfth O site, O is bonded in a distorted single-bond geometry to two equivalent Na and one H atom. In the thirteenth O site, O is bonded in a bent 120 degrees geometry to one Na and one O atom. In the fourteenth O site, O is bonded in a distorted water-like geometry to one Na and two H atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Yb5Cu11Sn8 by Materials Project

Yb5Cu11Sn8 crystallizes in the orthorhombic Pmmn space group. The structure is three-dimensional. there are three inequivalent Yb sites. In the first Yb site, Yb is bonded in a 2-coordinate geometry to ten Cu and six Sn atoms. There are a spread of Yb–Cu bond distances ranging from 3.00–3.50 Å. There are a spread of Yb–Sn bond distances ranging from 3.10–3.31 Å. In the second Yb site, Yb is bonded in a 3-coordinate geometry to eight Cu and eight Sn atoms. There are a spread of Yb–Cu bond distances ranging from 3.07–3.50 Å. There are a spread of Yb–Sn bond distances ranging from 3.17–3.73 Å. In the third Yb site, Yb is bonded in a 12-coordinate geometry to seven Cu and seven Sn atoms. There are a spread of Yb–Cu bond distances ranging from 3.03–3.34 Å. There are a spread of Yb–Sn bond distances ranging from 3.27–3.58 Å. There are six inequivalent Cu sites. In the first Cu site, Cu is bonded in a 8-coordinate geometry to four Yb and four Sn atoms. There are a spread of Cu–Sn bond distances ranging from 2.65–2.70 Å. In the second Cu site, Cu is bonded in a 8-coordinate geometry to four Yb and four Sn atoms. There are a spread of Cu–Sn bond distances ranging from 2.62–2.75 Å. In the third Cu site, Cu is bonded in a distorted body-centered cubic geometry to four Yb and four Sn atoms. There are two shorter (2.56 Å) and two longer (2.73 Å) Cu–Sn bond lengths. In the fourth Cu site, Cu is bonded in a 10-coordinate geometry to three Yb, three Cu, and four Sn atoms. There are one shorter (2.47 Å) and two longer (2.60 Å) Cu–Cu bond lengths. There are a spread of Cu–Sn bond distances ranging from 2.64–2.79 Å. In the fifth Cu site, Cu is bonded in a 8-coordinate geometry to three equivalent Yb, one Cu, and four Sn atoms. The Cu–Cu bond length is 2.53 Å. There are a spread of Cu–Sn bond distances ranging from 2.61–2.65 Å. In the sixth Cu site, Cu is bonded in a 10-coordinate geometry to four Yb, three Cu, and three Sn atoms. There are one shorter (2.60 Å) and two longer (2.63 Å) Cu–Sn bond lengths. There are five inequivalent Sn sites. In the first Sn site, Sn is bonded in a 9-coordinate geometry to five Yb and five Cu atoms. In the second Sn site, Sn is bonded in a 10-coordinate geometry to four Yb, five Cu, and one Sn atom. The Sn–Sn bond length is 3.07 Å. In the third Sn site, Sn is bonded in a 9-coordinate geometry to four Yb, six Cu, and one Sn atom. In the fourth Sn site, Sn is bonded to five Yb, six Cu, and one Sn atom to form distorted face-sharing SnYb5Cu6Sn cuboctahedra. The Sn–Sn bond length is 2.88 Å. In the fifth Sn site, Sn is bonded in a 10-coordinate geometry to five Yb, four Cu, and one Sn atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Ba3SrCoCu3O10 by Materials Project

Ba3SrCoCu3O10 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are twenty-four inequivalent Ba2+ sites. In the first Ba2+ site, Ba2+ is bonded in a 8-coordinate geometry to one Co4+, one Cu+2.67+, and seven O2- atoms. The Ba–Co bond length is 2.47 Å. The Ba–Cu bond length is 2.53 Å. There are a spread of Ba–O bond distances ranging from 2.42–3.10 Å. In the second Ba2+ site, Ba2+ is bonded in a 8-coordinate geometry to one Co4+, one Cu+2.67+, and six O2- atoms. The Ba–Co bond length is 2.44 Å. The Ba–Cu bond length is 2.47 Å. There are a spread of Ba–O bond distances ranging from 2.26–3.17 Å. In the third Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to one Co4+, one Cu+2.67+, and seven O2- atoms. The Ba–Co bond length is 2.42 Å. The Ba–Cu bond length is 2.50 Å. There are a spread of Ba–O bond distances ranging from 2.40–3.07 Å. In the fourth Ba2+ site, Ba2+ is bonded in a 8-coordinate geometry to one Co4+, one Cu+2.67+, and seven O2- atoms. The Ba–Co bond length is 2.49 Å. The Ba–Cu bond length is 2.48 Å. There are a spread of Ba–O bond distances ranging from 2.42–3.06 Å. In the fifth Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to one Co4+, one Cu+2.67+, and seven O2- atoms. The Ba–Co bond length is 2.48 Å. The Ba–Cu bond length is 2.49 Å. There are a spread of Ba–O bond distances ranging from 2.43–3.07 Å. In the sixth Ba2+ site, Ba2+ is bonded in a 7-coordinate geometry to two Cu+2.67+ and five O2- atoms. There are one shorter (2.40 Å) and one longer (2.55 Å) Ba–Cu bond lengths. There are a spread of Ba–O bond distances ranging from 2.27–2.76 Å. In the seventh Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to two Cu+2.67+ and seven O2- atoms. There are one shorter (2.44 Å) and one longer (2.52 Å) Ba–Cu bond lengths. There are a spread of Ba–O bond distances ranging from 2.36–3.21 Å. In the eighth Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to two Cu+2.67+ and seven O2- atoms. There are one shorter (2.43 Å) and one longer (2.54 Å) Ba–Cu bond lengths. There are a spread of Ba–O bond distances ranging from 2.31–3.17 Å. In the ninth Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to one Co4+, one Cu+2.67+, and seven O2- atoms. The Ba–Co bond length is 2.41 Å. The Ba–Cu bond length is 2.46 Å. There are a spread of Ba–O bond distances ranging from 2.35–3.06 Å. In the tenth Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to two Cu+2.67+ and seven O2- atoms. There are one shorter (2.45 Å) and one longer (2.55 Å) Ba–Cu bond lengths. There are a spread of Ba–O bond distances ranging from 2.33–3.14 Å. In the eleventh Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to one Co4+, one Cu+2.67+, and seven O2- atoms. The Ba–Co bond length is 2.45 Å. The Ba–Cu bond length is 2.51 Å. There are a spread of Ba–O bond distances ranging from 2.38–3.06 Å. In the twelfth Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to one Co4+, one Cu+2.67+, and seven O2- atoms. The Ba–Co bond length is 2.46 Å. The Ba–Cu bond length is 2.52 Å. There are a spread of Ba–O bond distances ranging from 2.31–3.12 Å. In the thirteenth Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to one Co4+, one Cu+2.67+, and seven O2- atoms. The Ba–Co bond length is 2.43 Å. The Ba–Cu bond length is 2.53 Å. There are a spread of Ba–O bond distances ranging from 2.42–3.04 Å. In the fourteenth Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to two Cu+2.67+ and seven O2- atoms. There are one shorter (2.45 Å) and one longer (2.51 Å) Ba–Cu bond lengths. There are a spread of Ba–O bond distances ranging from 2.46–3.14 Å. In the fifteenth Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to one Co4+, one Cu+2.67+, and seven O2- atoms. The Ba–Co bond length is 2.49 Å. The Ba–Cu bond length is 2.53 Å. There are a spread of Ba–O bond distances ranging from 2.44–3.12 Å. In the sixteenth Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to one Co4+, one Cu+2.67+, and seven O2- atoms. The Ba–Co bond length is 2.46 Å. The Ba–Cu bond length is 2.51 Å. There are a spread of Ba–O bond distances ranging from 2.43–3.08 Å. In the seventeenth Ba2+ site, Ba2+ is bonded in a 7-coordinate geometry to one Co4+, one Cu+2.67+, and seven O2- atoms. The Ba–Co bond length is 2.45 Å. The Ba–Cu bond length is 2.52 Å. There are a spread of Ba–O bond distances ranging from 2.39–3.21 Å. In the eighteenth Ba2+ site, Ba2+ is bonded in a 7-coordinate geometry to two Cu+2.67+ and seven O2- atoms. There are one shorter (2.40 Å) and one longer (2.59 Å) Ba–Cu bond lengths. There are a spread of Ba–O bond distances ranging from 2.26–3.23 Å. In the nineteenth Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to two Cu+2.67+ and seven O2- atoms. There are one shorter (2.45 Å) and one longer (2.56 Å) Ba–Cu bond lengths. There are a spread of Ba–O bond distances ranging from 2.31–3.16 Å. In the twentieth Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to two Cu+2.67+ and seven O2- atoms. There are one shorter (2.47 Å) and one longer (2.55 Å) Ba–Cu bond lengths. There are a spread of Ba–O bond distances ranging from 2.30–3.25 Å. In the twenty-first Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to one Co4+, one Cu+2.67+, and seven O2- atoms. The Ba–Co bond length is 2.40 Å. The Ba–Cu bond length is 2.52 Å. There are a spread of Ba–O bond distances ranging from 2.36–3.17 Å. In the twenty-second Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to one Co4+, one Cu+2.67+, and seven O2- atoms. The Ba–Co bond length is 2.45 Å. The Ba–Cu bond length is 2.53 Å. There are a spread of Ba–O bond distances ranging from 2.38–3.08 Å. In the twenty-third Ba2+ site, Ba2+ is bonded in a 8-coordinate geometry to two Cu+2.67+ and seven O2- atoms. There are one shorter (2.45 Å) and one longer (2.55 Å) Ba–Cu bond lengths. There are a spread of Ba–O bond distances ranging from 2.34–3.22 Å. In the twenty-fourth Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to one Co4+, one Cu+2.67+, and seven O2- atoms. The Ba–Co bond length is 2.47 Å. The Ba–Cu bond length is 2.52 Å. There are a spread of Ba–O bond distances ranging from 2.39–3.12 Å. There are eight inequivalent Sr2+ sites. In the first Sr2+ site, Sr2+ is bonded in a 3-coordinate geometry to two Cu+2.67+ and seven O2- atoms. There are one shorter (2.34 Å) and one longer (2.66 Å) Sr–Cu bond lengths. There are a spread of Sr–O bond distances ranging from 2.16–3.10 Å. In the second Sr2+ site, Sr2+ is bonded in a 1-coordinate geometry to two Cu+2.67+ and seven O2- atoms. There are one shorter (2.33 Å) and one longer (2.64 Å) Sr–Cu bond lengths. There are a spread of Sr–O bond distances ranging from 2.16–3.11 Å. In the third Sr2+ site, Sr2+ is bonded in a 5-coordinate geometry to one Co4+, one Cu+2.67+, and seven O2- atoms. The Sr–Co bond length is 2.40 Å. The Sr–Cu bond length is 2.52 Å. There are a spread of Sr–O bond distances ranging from 2.21–3.14 Å. In the fourth Sr2+ site, Sr2+ is bonded in a 7-coordinate geometry to two Cu+2.67+ and five O2- atoms. There are one shorter (2.36 Å) and one longer (2.58 Å) Sr–Cu bond lengths. There are a spread of Sr–O bond distances ranging from 2.19–2.72 Å. In the fifth Sr2+ site, Sr2+ is bonded in a 7-coordinate geometry to two Cu+2.67+ and five O2- atoms. There are one shorter (2.33 Å) and one longer (2.62 Å) Sr–Cu bond lengths. There are a spread of Sr–O bond distances ranging from 2.18–2.80 Å. In the sixth Sr2+ site, Sr2+ is bonded in a 1-coordinate geometry to two Cu+2.67+ and six O2- atoms. There are one shorter (2.40 Å) and one longer (2.63 Å) Sr–Cu bond lengths. There are a spread of Sr–O bond distances ranging from 2.12–2.98 Å. In the seventh Sr2+ site, Sr2+ is bonded in a 5-coordinate geometry to two Cu+2.67+ and seven O2- atoms. There are one shorter (2.37 Å) and one longer (2.54 Å) Sr–Cu bond lengths. There are a spread of Sr–O bond distances ranging from 2.26–3.12 Å. In the eighth Sr2+ site, Sr2+ is bonded in a 5-coordinate geometry to one Cu+2.67+ and five O2- atoms. The Sr–Cu bond length is 2.59 Å. There are a spread of Sr–O bond distances ranging from 2.22–2.63 Å. There are eight inequivalent Co4+ sites. In the first Co4+ site, Co4+ is bonded in a 4-coordinate geometry to two Ba2+ and four O2- atoms. There are a spread of Co–O bond distances ranging from 1.85–2.30 Å. In the second Co4+ site, Co4+ is bonded in a 4-coordinate geometry to one Ba2+, one Sr2+, and four O2- atoms. There are a spread of Co–O bond distances ranging from 1.84–2.24 Å. In the third Co4+ site, Co4+ is bonded in a 4-coordinate geometry to two Ba2+ and five O2- atoms. There are a spread of Co–O bond distances ranging from 1.86–2.69 Å. In the fourth Co4+ site, Co4+ is bonded in a distorted rectangular see-saw-like geometry to two Ba2+ and four O2- atoms. There are a spread of Co–O bond distances ranging from 1.85–2.12 Å. In the fifth Co4+ site, Co4+ is bonded in a 3-coordinate geometry to two Ba2+ and four O2- atoms. There are a spread of Co–O bond distances ranging from 1.87–2.36 Å. In the sixth Co4+ site, Co4+ is bonded in a 4-coordinate geometry to two Ba2+ and five O2- atoms. There are a spread of Co–O bond distances ranging from 1.81–2.53 Å. In the seventh Co4+ site, Co4+ is bonded in a 4-coordinate geometry to two Ba2+ and five O2- atoms. There are a spread of Co–O bond distances ranging from 1.84–2.66 Å. In the eighth Co4+ site, Co4+ is bonded in a 4-coordinate geometry to two Ba2+ and four O2- atoms. There are a spread of Co–O bond distances ranging from 1.77–2.24 Å. There are twenty-four inequivalent Cu+2.67+ sites. In the first Cu+2.67+ site, Cu+2.67+ is bonded in a 4-coordinate geometry to one Ba2+, one Sr2+, and five O2- atoms. There are a spread of Cu–O bond distances ranging from 1.96–2.55 Å. In the second Cu+2.67+ site, Cu+2.67+ is bonded in a distorted rectangular see-saw-like geometry to two Ba2+ and four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.96–2.07 Å. In the third Cu+2.67+ site, Cu+2.67+ is bonded in a distorted rectangular see-saw-like geometry to one Ba2+, one Sr2+, and five O2- atoms. There are a spread of Cu–O bond distances ranging from 1.98–2.55 Å. In the fourth Cu+2.67+ site, Cu+2.67+ is bonded in a 4-coordinate geometry to one Ba2+, one Sr2+, and four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.96–2.20 Å. In the fifth Cu+2.67+ site, Cu+2.67+ is bonded in a distorted rectangular see-saw-like geometry to one Ba2+, one Sr2+, and four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.94–2.10 Å. In the sixth Cu+2.67+ site, Cu+2.67+ is bonded in a 4-coordinate geometry to one Ba2+, one Sr2+, and four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.92–2.21 Å. In the seventh Cu+2.67+ site, Cu+2.67+ is bonded in a 4-coordinate geometry to one Sr2+ and four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.92–2.18 Å. In the eighth Cu+2.67+ site, Cu+2.67+ is bonded in a distorted rectangular see-saw-like geometry to two Ba2+ and four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.97–2.12 Å. In the ninth Cu+2.67+ site, Cu+2.67+ is bonded in a 2-coordinate geometry to one Ba2+, one Sr2+, and four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.79–2.26 Å. In the tenth Cu+2.67+ site, Cu+2.67+ is bonded in a 2-coordinate geometry to two Ba2+ and four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.85–2.34 Å. In the eleventh Cu+2.67+ site, Cu+2.67+ is bonded in a 6-coordinate geometry to two Ba2+ and four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.87–2.26 Å. In the twelfth Cu+2.67+ site, Cu+2.67+ is bonded in a 6-coordinate geometry to one Ba2+, one Sr2+, and four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.88–2.28 Å. In the thirteenth Cu+2.67+ site, Cu+2.67+ is bonded in a 2-coordinate geometry to two Ba2+ and four O2- atoms. There are a spread of Cu–O bond distances rangi

36 MATERIALS SCIENCE↗
DOE OSTI2022

Exploration of the bio-analogous asymmetric C–C coupling mechanism in tandem CO 2 electroreduction

C–C coupling is a critical step of CO 2 fixation in constructing the carbon skeleton of value-added multicarbon products. The Wood–Ljungdahl pathway is an efficient natural process through which microbes transform CO 2 into methyl and carbonyl groups and subsequently couple them together. This asymmetric coupling mechanism remains largely unexplored in inorganic CO 2 electroreduction. Here we experimentally validate the asymmetric coupling pathway through isotope-labelled co-reduction experiments on a Cu surface where 13 CH 3 I and 12 CO are co-fed externally as the methyl and the carbonyl source, respectively. Isotope-labelled multicarbon oxygenates were detected, which confirms an electrocatalytic asymmetric coupling on the Cu surface. We further employed tandem Cu–Ag nanoparticle systems in which *CH x and *CO intermediates can be generated to achieve asymmetric C–C coupling for a practical CO 2 electroreduction. We found that the production of multicarbon oxygenates is correlated with the generation rate of two intermediate indicators, CH 4 and CO. By aligning their rates, the oxygenates generation rate can be maximized.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗