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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Giant topological Hall effect in centrosymmetric tetragonal Mn 2–x Zn x Sb

Topological magnetism typically appears in noncentrosymmetric compounds or compounds with geometric frustration. Here, we report the effective tuning of magnetism in centrosymmetric tetragonal Mn 2–x Zn x Sb by Zn substitution. The magnetism is found to be closely coupled to the transport properties, giving rise to a very large topological Hall effect with fine-tuning of Zn content, which even persists to high temperature (~250K). The further magnetoentropic analysis suggests that the topological Hall effect is possibly associated with topological magnetism. Furthermore, our finding suggests Mn 2–x Zn x S is a candidate material for a centrosymmetric tetragonal topological magnetic system, offering opportunities for studying and tuning spin textures and developing near room temperature spin-based devices.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Structural mechanism of intracellular autoregulation of zinc uptake in ZIP transporters

Abstract Zinc is an essential micronutrient that supports all living organisms through regulating numerous biological processes. However, the mechanism of uptake regulation by intracellular Zn 2+ status remains unclear. Here we report a cryo-electron microscopy structure of a ZIP-family transporter from Bordetella bronchiseptica at 3.05 Å resolution in an inward-facing, inhibited conformation. The transporter forms a homodimer, each protomer containing nine transmembrane helices and three metal ions. Two metal ions form a binuclear pore structure, and the third ion is located at an egress site facing the cytoplasm. The egress site is covered by a loop, and two histidine residues on the loop interact with the egress-site ion and regulate its release. Cell-based Zn 2+ uptake and cell growth viability assays reveal a negative regulation of Zn 2+ uptake through sensing intracellular Zn 2+ status using a built-in sensor. These structural and biochemical analyses provide mechanistic insight into the autoregulation of zinc uptake across membranes.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Effects of Metal and Metal Ion on Biomethane Productivity during Anaerobic Digestion of Dairy Manure

To overcome major limiting factors of microbial processes in anaerobic digestion (AD), metal and metal ions have been extensively studied. However, there is confusion about the effects of metals and metal ions on biomethane productivity in previous research. In this study, Zn and Zn 2+ were selected as representatives of metals and metal ions, respectively, to investigate the effects on biomethane productivity. After the metals and metal ions at different concentrations were added to the batch AD experiments under the same mesophilic conditions, a Zn dose of 1 g/L and a Zn 2+ dose of 4 mg/L were found to cause the highest biomethane production, respectively. The results indicate that metal (Zn) and metal ion (Zn 2+ ) have different mechanisms to improve AD performance. There may be two possible explanations. To act as conductive materials in interspecies electron transfer (IET), relatively high doses of metals (e.g., 1 g/L of Zn, 10 g/L of Fe) are needed to bridge the electron transfer from syntrophic bacteria to methanogenic archaea in the AD process. As essential mineral nutrients, the AD system requires relatively low doses of metal ions (e.g., 4 mg/L of Zn 2+ , 5 mg/L of Fe 2+ ) to supplement the component of various enzymes that catalyze anaerobic reactions and transformations. This research will provide clear insight for selecting appropriate amounts of metals or metal ions to enhance biomethane productivity for industrial AD processes.

09 BIOMASS FUELS↗
DOE OSTI2023

Understanding the Surprising Ionic Conductivity Maximum in Zn(TFSI) 2 Water/Acetonitrile Mixture Electrolytes

Aqueous electrolytes composed of 0.1 M zinc bis-(trifluoromethyl-sulfonyl)-imide (Zn-(TFSI) 2 ) and acetonitrile (ACN) were studied using combined experimental and simulation techniques. The electrolyte was found to be electrochemically stable when the ACN V% is higher than 74.4. In addition, it was found that the ionic conductivity of the mixed solvent electrolytes changes as a function of ACN composition, and a maximum was observed at 91.7 V% of ACN although the salt concentration is the same. This behavior was qualitatively reproduced by molecular dynamics (MD) simulations. Detailed analyses based on experiments and MD simulations show that at high ACN composition the water network existing in the high water composition solutions breaks. As a result, the screening effect of the solvent weakens and the correlation among ions increases, which causes a decrease in ionic conductivity at high ACN V%. Furthermore, this study provides a fundamental understanding of this complex mixed solvent electrolyte system.

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

Potentiodynamics of the Zinc and Proton Storage in Disordered Sodium Vanadate for Aqueous Zn-Ion Batteries

A rechargeable Zn-ion battery is a promising aqueous system, where coinsertion of Zn 2+ and H + could address the obstacles of the sluggish ionic transport in cathode materials imposed by multivalent battery chemistry. However, there is a lack of fundamental understanding of this dual-ion transport, especially the potentiodynamics of the storage process. Here, a quantitative analysis of Zn 2+ and H + transport in a disordered sodium vanadate (NaV 3 O 8 ) cathode material has been reported. Collectively, synchrotron X-ray analysis shows that both Zn 2+ and H + storages follow an intercalation storage mechanism in NaV 3 O 8 and proceed in a sequential manner, where intercalations of 0.26 Zn 2+ followed by 0.24 H + per vanadium atom occur during discharging, while reverse dynamics happens during charging. We find that such a unique and synergistic dual-ion sequential storage favors a high capacity (265 mA h g –1 ) and an energy density (221 W h kg –1 ) based on the NaV 3 O 8 cathode and a great cycling life (a capacity retention of 78% after 2000 cycles) in Zn/NaV 3 O 8 full cells.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Synthesis and characterization of the novel breathing pyrochlore compound Ba 3 ⁢Tm 2⁢ Zn 5⁢ O 11

In this study, a novel material from the rare-earth based breathing pyrochlore family, Ba 3 ⁢Tm 2 ⁢Zn 5 ⁢O 11 , was successfully synthesized. Powder x-ray diffraction and high-resolution powder neutron diffraction confirmed phase purity and the $F\bar4$3⁢𝑚 breathing pyrochlore crystal structure, while thermogravimetric analysis revealed incongruent melting behavior compared to its counterpart, Ba 3 ⁢Yb 2⁢ Zn 5⁢ O 11 . High-quality single crystals of Ba 3 ⁢Tm 2 ⁢Zn 5 ⁢O 11 were grown using the traveling solvent floating zone technique and assessed using Laue x-ray diffraction and single crystal x-ray diffraction. Further, thermodynamic characterization indicated paramagnetic behavior down to 0.05 K, and inelastic neutron scattering measurements identified distinct dispersionless crystal electric field energy bands, with the fitted crystal electric field model predicting a single-ion singlet ground state and an energy gap of ∼9 meV separating it from the first excited (singlet) state. Additional low-energy excitation studies on single crystals revealed dispersionless bands at 0.8 and 1 meV. Computed phonon dispersions from first-principles calculations ruled out phonons as the origin of these modes, further illustrating the puzzling and unique properties of Ba 3 ⁢Tm⁢ 2 Zn 5 ⁢O 11 .

36 MATERIALS SCIENCE↗
DOE OSTI2022

Ultrafast Metal Electrodeposition Revealed by In Situ Optical Imaging and Theoretical Modeling towards Fast–Charging Zn Battery Chemistry

Metallic Zn is a preferred anode material for rechargeable aqueous batteries towards a smart grid and renewable energy storage. Importantly, understanding how the metal nucleates and grows at the aqueous Zn anode is a critical and challenging step to achieve full reversibility of Zn battery chemistry, especially under fast-charging conditions. Here, by combining in situ optical imaging and theoretical modeling, we uncover the critical parameters governing the electrodeposition stability of the metallic Zn electrode, that is, the competition among crystallographic thermodynamics, kinetics, and Zn 2+ -ion diffusion. Moreover, steady-state Zn metal plating/ stripping with Coulombic efficiency above 99 % is achieved at 10-100 mA cm -2 in a reasonably high concentration (3 M) ZnSO 4 electrolyte. Significantly, a long-term cycling-stable Zn metal electrode is realized with a depth of discharge of 66.7% under 50 mA cm -2 in both Zn || Zn symmetrical cells and MnO 2 || Zn full cells.

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

Mechanistic Investigation of Redox Processes in Zn-MnO2 battery in Mild Aqueous Electrolytes

Zinc-MnO2 based batteries have acquired attention for grid-level applications, due to impressive theoretical performance, cost effectiveness and intrinsic safety. However, there are still many challenges that remain elusive due to the complex and controversial mechanisms of operation that hinders commercialization. In this work, the detailed redox processes that occur at the cathode during Zn-MnO2 battery operation are elucidated. Using a blend of structural and electrochemical techniques, the redox pairs that occur during operation are mechanistically studied while also showcasing the true impact of the electrolyte additive (0.1 M MnSO4) in a 1 M ZnSO4 electrolyte. An electrochemical quartz-crystal microbalance (EQCM) has been leveraged to reveal the effect of zinc hydroxy sulfate salt (Zn4SO4(OH)6·nH2O) and zinc manganese oxide (ZnxMnyOz) dissolution/deposition, which are believed to be major components during discharge and charge conditions. . These results provide insight not currently available, allowing a holistic view of the electrochemical reaction mechanisms during battery operation.

Rodriguez Perez, Ismael A.↗
DOE OSTI2025

BaCu 4/3 Si 2/3 P 2 and BaCu 2–( x + y ) Zn x Si y P 2 : Expanding the Semiconducting Landscape in the ThCr 2 Si 2 -Type Family

ThCr 2 Si 2 -type layered materials are a large family of compounds with applications ranging from thermoelectricity to magnetism, with the vast majority of the members exhibiting metallic behavior. Here, in this study, we synthesized a new group of materials with Cu-Si and Cu-Zn-Si square nets with the general formula BaCu 1.33 Si 0.67 P 2 and BaCu 2–(x+y) Zn x Si y P 2 (0 ≤ x ≤ 0.9; 0.3 ≤ y ≤ 0.7). Several synthesized compounds are charge-balanced semiconductors, which are rare in the ThCr 2 Si 2 family. All the reported compounds crystallize in the ThCr 2 Si 2 -type tetragonal I4/mmm space group, with Cu/Zn/Si jointly occupying the same 4d crystallographic site. In the Zn-free composition, BaCu 1.33 Si 0.67 P 2 , Ba, and P each occupy a single crystallographic site. The introduction of Zn results in the expansion of the unit cell and splitting the Ba atomic sites along the [001] direction. Such structural displacement of the Ba atoms was confirmed by the heat capacity measurements. Band structure and density-of-states calculations on ordered hypothetical structural models reveal either a small bandgap (∼0.2 eV) or semimetallic band structures. The compounds reported here exhibit high Seebeck coefficients and ultralow thermal conductivity, making them promising candidates for the development of thermoelectric materials.

crystal structure↗
DOE OSTI2021

A lipoprotein allosterically activates the CwlD amidase during Clostridioides difficile spore formation

Spore-forming pathogens like Clostridioides difficile depend on germination to initiate infection. During gemination, spores must degrade their cortex layer, which is a thick, protective layer of modified peptidoglycan. Cortex degradation depends on the presence of the spore-specific peptidoglycan modification, muramic-∂-lactam (MAL), which is specifically recognized by cortex lytic enzymes. In C . difficile , MAL production depends on the CwlD amidase and its binding partner, the GerS lipoprotein. To gain insight into how GerS regulates CwlD activity, we solved the crystal structure of the CwlD:GerS complex. In this structure, a GerS homodimer is bound to two CwlD monomers such that the CwlD active sites are exposed. Although CwlD structurally resembles amidase_3 family members, we found that CwlD does not bind Zn 2+ stably on its own, unlike previously characterized amidase_3 enzymes. Instead, GerS binding to CwlD promotes CwlD binding to Zn 2+ , which is required for its catalytic mechanism. Thus, in determining the first structure of an amidase bound to its regulator, we reveal stabilization of Zn 2+ co-factor binding as a novel mechanism for regulating bacterial amidase activity. Our results further suggest that allosteric regulation by binding partners may be a more widespread mode for regulating bacterial amidase activity than previously thought.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Role of Histidine‐Containing Peptoids in Accelerating the Kinetics of Calcite Growth

Carbonate mineralization, the conversion of CO 2 into stable, thermodynamically favorable carbonate minerals, offers a promising strategy for permanent and environmentally friendly carbon storage, with minimal risk of long-term leakage and minimal monitoring requirements. Drawing inspiration from carbonic anhydrase (CA), a family of zinc-containing metalloenzymes that catalyze the hydration of CO 2 to bicarbonate and promote carbonate precipitation, a class of histidine-containing peptoids was designed that is capable of coordinating with Zn 2+ ions to act as CA mimetics for accelerating calcite step growth. In situ atomic force microscopy (AFM) measurements reveal that these peptoids significantly enhance step advancement, with a more pronounced effect observed when combined with Zn 2+ ions and under higher calcium-to-carbonate activity ratios, indicating that peptoids facilitate the incorporation of CO 3 2− ions at step edges. Solution NMR and 3D atomic force microscopy (3D AFM) analyses show that the coordination of peptoids with Zn 2+ promotes both the deprotonation of HCO 3 − to CO 3 2− and restructures the interfacial hydration layers of calcite, collectively lowering the activation barrier for step growth. These findings establish a design framework for sequence-defined polymers to regulate carbonate mineralization, offering promising applications in CO 2 capture and long-term storage.

CO2 mineralization↗
DOE OSTI2026

Inter-ligand cross-links determine secondary building unit formation in oligoMOFs

OligoMOFs are a class of metal–organic frameworks (MOFs) that feature ligands covalently cross-linked into oligomers as intrinsic structural components. A recent study has demonstrated that the size and flexibility of the tether moieties can result in the formation of oligoMOFs with different isomeric structures via geometrical distortions in the secondary building unit (SBU). In this work, it is demonstrated that tethered dimeric ligands with slightly different carbon chain lengths can direct the formation of oligoMOFs with SBUs of different structure and nuclearity. Specifically, inter-ligand cross links are used as a sensitive probe of the phase landscape of MOFs with the composition [Zn 2 (R-bdc) 2 (bpy)] (bdc = 1,4-benzenedicarboxylate, bpy = 4,4′-bipyridine), showing that a hexyl tether results in a framework structure identical to MOF-508, based on dinuclear {Zn 2 } “paddlewheel” SBUs, while heptyl and octyl tethers result in a “honeycomb-like” framework structure based on an infinite rod-like Zn 2+ SBU bridged by carboxylate ligands. Furthermore, these results are the first examples of tether length influencing SBU chemistry in MOFs and help understand the interplay between the MOF lattice and the geometric constraints imposed by inter-ligand cross-links in oligoMOFs.

MOFs↗
DOE OSTI2025

Observation of Topological Spin Textures in Ferrimagnetic Mn 2 − x Zn x Sb

Ferrimagnets, which have both ferromagnetic and antiferromagnetic coupling, are attracting increased attention in the realm of spintronic devices due to advantages such as ultrafast dynamics and a suppressed skyrmion Hall effect. Thus, understanding the behavior of nontrivial spin textures in ferrimagnets is crucial; however, comprehensive reports on this topic remain limited. Here, the magnetic spin textures of ferrimagnetic Mn 2 − x Zn x Sb (x = 0.85) is explored as a function of temperature and applied magnetic field. The spin textures can be tuned to a variety of states, including stripes, skyrmion bags, and a skyrmion lattice. Chiral Néel-type magnetic structures are visualized using Lorentz transmission electron microscopy. Mn(I) ions are slightly shifted toward the Sb sites, which may be due to a strong electrostatic interaction between Mn and Sb ions. This local structural distortion breaks the inversion symmetry and introduces an effective Dzyaloshinkii–Moriya interaction. This work thus provides a pathway to use doping and heterogeneity in a ferrimagnet to control and generate chiral nontrivial spin textures.

Mn ion displacement↗
DOE OSTI2020

Tailoring SnO 2 , (Mg,Zn)O, and Ga:(Mg,Zn)O electro-optical properties and stability for solar cells

The electron density, mobility, bandgap, and band alignment of transparent conducting oxides (TCOs) can be tailored by adjusting composition and stoichiometry, thereby enabling interface engineering for diverse semiconductor applications. For example, solar cell efficiency can change enormously by adjusting TCO properties. At the same time, these TCO properties can shift during the deposition of other layers, anneals, and device operation. An ideal TCO should have tunable but stable electro-optical properties. Here, we deposit SnO 2 , (Mg,Zn)O (MZO), and Ga:(Mg,Zn)O (GMZO) films on glass and measure electro-optical characteristics before and after reducing, inert, oxidizing, and CdCl2 anneals over a range of temperatures. Electron density generally increases in the progression from oxidizing to inert and reducing ambients. SnO 2 is relatively stable compared to MZO but has less flexibility for interface engineering. We investigate GMZO as a similar but more stable alternative to MZO.The addition of Ga to MZO has significant effects on electron density and improves electro-optical stability, which can be advantageous for semiconductor applications. Furthermore, we demonstrate that GMZO can be readily incorporated into solar cells.

14 SOLAR ENERGY↗
DOE OSTI2023

Enhanced Thermoelectric Properties of Heavy-fermion Compounds $\text{Yb}_x\text{Ce}_y\text{Sm}_z\text{Ir}_2\text{Zn}_{20}$ $(x+y+z=1)$

Herein, thermoelectric materials hold tremendous promise for advances in fundamental science and practical ap- plications, particularly for robust electricity generation in extreme and remote environments. Despite this, for most materials the energy conversion efficiency is limited by the proportionality between the electrical and thermal conductivities and small values of the Seebeck coefficient for metals. It was previously reported that the heavy-fermion compound $\text{YbIr}_2$ $\text{Zn}_{20}$ exhibits large Seebeck coefficient and thermoelectric figure of merit $ZT$ at 35 K. This behavior is primarily associated with strong hybridization between the $f$- and conduction electron states. Here, we seek to improve the thermoelectric properties through chemical substitution on the Yb site using Ce and Sm. By surveying different levels of substitution, we find that the thermoelectric properties vary strongly with the $f$-element ratio. This confirms that electronic hybridization dominates the thermoelectric properties and clarifies directions for optimizing these materials for applications. We also investigate the impact of the disorder on the thermal conductivity, where we find only weak variation with lanthanide content.

36 MATERIALS SCIENCE↗
NASA NTRS1990

Electronic state and superconductivity of YBa2Cu3-xO7-y (M=Al,Zn and Sn) systems

A series of YBa2Cu(3-x)MxO(7-y) (M=Al,Zn and Sn) single phase samples were prepared, and the measurements of the crystal structure, oxygen content, electric resistivity, thermoelectric power, Mossbauer spectrum, XPS and superconductivity were performed. The experimental results of X ray powder diffraction, Mossbauer spectrum and oxygen content show that the Zn(2+) and the Al(3+) occupy the Cu(2) site in Cu-O planes and the Cu(1) site in Cu-O chains respectively, but the Sn(4+) occupies both the Cu(1) sites. As regards the properties in superconducting state, both the Zn(2+) and the Al(3+) depress T(sub c) strongly, but the Sn(4+) does not. As for the electronic transport properties in normal state, the system doped by Al(3+) displays a rapid increase of resistivity and some electron localization-like effects, and the thermoelectric power enhances obviously; the series contained Zn(2+) almost shows no changes of electric resistivity but the sign of the thermoelectric power is reversed. Other results are given and briefly discussed.

Zhao, Y.↗
DOE OSTI2020

Materials Data on Zn(Bi19O30)2 by Materials Project

Bi38ZnO60 crystallizes in the trigonal P3 space group. The structure is three-dimensional. Zn is bonded to four O atoms to form ZnO4 tetrahedra that share corners with twelve BiO5 square pyramids. There are three shorter (2.03 Å) and one longer (2.05 Å) Zn–O bond lengths. There are fourteen inequivalent Bi sites. In the first Bi site, Bi is bonded to five O atoms to form distorted BiO5 square pyramids that share corners with eight BiO5 square pyramids, a cornercorner with one ZnO4 tetrahedra, and an edgeedge with one BiO5 square pyramid. There are a spread of Bi–O bond distances ranging from 2.10–2.67 Å. In the second Bi site, Bi is bonded to five O atoms to form distorted BiO5 square pyramids that share corners with eight BiO5 square pyramids, a cornercorner with one BiO4 tetrahedra, and an edgeedge with one BiO5 square pyramid. There are a spread of Bi–O bond distances ranging from 2.11–2.65 Å. In the third Bi site, Bi is bonded to five O atoms to form distorted BiO5 square pyramids that share corners with eight BiO5 square pyramids, a cornercorner with one ZnO4 tetrahedra, and an edgeedge with one BiO5 square pyramid. There are a spread of Bi–O bond distances ranging from 2.12–2.69 Å. In the fourth Bi site, Bi is bonded to five O atoms to form distorted BiO5 square pyramids that share corners with eight BiO5 square pyramids, a cornercorner with one BiO4 tetrahedra, and an edgeedge with one BiO5 square pyramid. There are a spread of Bi–O bond distances ranging from 2.10–2.72 Å. In the fifth Bi site, Bi is bonded to five O atoms to form distorted BiO5 square pyramids that share corners with eight BiO5 square pyramids, a cornercorner with one BiO4 tetrahedra, and an edgeedge with one BiO5 square pyramid. There are a spread of Bi–O bond distances ranging from 2.12–2.70 Å. In the sixth Bi site, Bi is bonded to five O atoms to form distorted BiO5 square pyramids that share corners with eight BiO5 square pyramids, a cornercorner with one ZnO4 tetrahedra, and an edgeedge with one BiO5 square pyramid. There are a spread of Bi–O bond distances ranging from 2.11–2.67 Å. In the seventh Bi site, Bi is bonded to four O atoms to form corner-sharing BiO4 tetrahedra. There are one shorter (2.04 Å) and three longer (2.05 Å) Bi–O bond lengths. In the eighth Bi site, Bi is bonded to five O atoms to form distorted BiO5 square pyramids that share corners with eight BiO5 square pyramids, a cornercorner with one ZnO4 tetrahedra, and an edgeedge with one BiO5 square pyramid. There are a spread of Bi–O bond distances ranging from 2.11–2.69 Å. In the ninth Bi site, Bi is bonded to five O atoms to form distorted BiO5 square pyramids that share corners with eight BiO5 square pyramids, a cornercorner with one BiO4 tetrahedra, and an edgeedge with one BiO5 square pyramid. There are a spread of Bi–O bond distances ranging from 2.12–2.72 Å. In the tenth Bi site, Bi is bonded to five O atoms to form distorted BiO5 square pyramids that share corners with eight BiO5 square pyramids, a cornercorner with one BiO4 tetrahedra, and an edgeedge with one BiO5 square pyramid. There are a spread of Bi–O bond distances ranging from 2.10–2.66 Å. In the eleventh Bi site, Bi is bonded to five O atoms to form distorted BiO5 square pyramids that share corners with eight BiO5 square pyramids, a cornercorner with one BiO4 tetrahedra, and an edgeedge with one BiO5 square pyramid. There are a spread of Bi–O bond distances ranging from 2.12–2.71 Å. In the twelfth Bi site, Bi is bonded to five O atoms to form distorted BiO5 square pyramids that share corners with eight BiO5 square pyramids, a cornercorner with one BiO4 tetrahedra, and an edgeedge with one BiO5 square pyramid. There are a spread of Bi–O bond distances ranging from 2.11–2.64 Å. In the thirteenth Bi site, Bi is bonded to five O atoms to form distorted BiO5 square pyramids that share corners with eight BiO5 square pyramids, a cornercorner with one BiO4 tetrahedra, and an edgeedge with one BiO5 square pyramid. There are a spread of Bi–O bond distances ranging from 2.11–2.67 Å. In the fourteenth Bi site, Bi is bonded to four O atoms to form corner-sharing BiO4 tetrahedra. There are three shorter (2.04 Å) and one longer (2.05 Å) Bi–O bond lengths. There are twenty-four inequivalent O sites. In the first O site, O is bonded in a trigonal non-coplanar geometry to three Bi atoms. In the second O site, O is bonded in a trigonal planar geometry to three Bi atoms. In the third O site, O is bonded in a distorted trigonal non-coplanar geometry to three Bi atoms. In the fourth O site, O is bonded in a trigonal non-coplanar geometry to three Bi atoms. In the fifth O site, O is bonded in a trigonal planar geometry to three Bi atoms. In the sixth O site, O is bonded in a distorted trigonal non-coplanar geometry to three Bi atoms. In the seventh O site, O is bonded to four Bi atoms to form distorted corner-sharing OBi4 tetrahedra. In the eighth O site, O is bonded in a distorted trigonal non-coplanar geometry to three Bi atoms. In the ninth O site, O is bonded in a distorted trigonal non-coplanar geometry to three Bi atoms. In the tenth O site, O is bonded in a distorted trigonal non-coplanar geometry to three Bi atoms. In the eleventh O site, O is bonded in a distorted trigonal non-coplanar geometry to three Bi atoms. In the twelfth O site, O is bonded to one Zn and three Bi atoms to form corner-sharing OZnBi3 tetrahedra. In the thirteenth O site, O is bonded to four Bi atoms to form distorted corner-sharing OBi4 tetrahedra. In the fourteenth O site, O is bonded in a distorted trigonal non-coplanar geometry to three Bi atoms. In the fifteenth O site, O is bonded in a distorted trigonal non-coplanar geometry to three Bi atoms. In the sixteenth O site, O is bonded in a trigonal non-coplanar geometry to three Bi atoms. In the seventeenth O site, O is bonded in a distorted trigonal non-coplanar geometry to three Bi atoms. In the eighteenth O site, O is bonded in a trigonal planar geometry to three Bi atoms. In the nineteenth O site, O is bonded in a trigonal planar geometry to three equivalent Bi atoms. In the twentieth O site, O is bonded in a trigonal planar geometry to three equivalent Bi atoms. In the twenty-first O site, O is bonded to four Bi atoms to form distorted corner-sharing OBi4 tetrahedra. In the twenty-second O site, O is bonded to four Bi atoms to form corner-sharing OBi4 tetrahedra. In the twenty-third O site, O is bonded to one Zn and three equivalent Bi atoms to form corner-sharing OZnBi3 tetrahedra. In the twenty-fourth O site, O is bonded in a trigonal planar geometry to three equivalent Bi atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2024

AP-XPS Study of the Reaction of O 2 and CO 2 with Zn–Au(111) Surface Alloys: Activation of O–O/C–O Bonds and the Formation of ZnO

Synchrotron-based ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) was used to study the dissociation of O 2 and CO 2 on Zn-Au(111) alloys which contained 0.2-0.3 monolayers of zinc. Although Au(111) is inert, the alloys displayed a high activity for the cleavages of O-O and C-O bonds at room temperature with the formation of ZnO x species. Dissociative adsorption of O 2 at 300 K destroyed the alloys and the results of AP-XPS pointed to the co-existence of two types of oxygen species on the surface: ZnO x and chemisorbed O atoms (O chem ) on Au or the Au-ZnO interface. Annealing from room temperature to 600 K induced a O chem → ZnO x transformation that reflected the poor stability of O atoms on Au(111). The Zn-Au(111) systems exhibited a reactivity towards CO 2 that was much larger than that seen for Au(111), Cu(111) or surfaces of late transition metals like, Ni, Pd or Pt. At 300 K, CO 2 underwent partial dissociation depositing large amounts of O chem on the surface with minor formation of ZnO x . In addition, the deposited O chem reacted with CO 2 to form surface carbonate groups. Dosing of CO 2 at 500-600 K mainly led to the formation of ZnO x and the surface carbonate almost disappeared. In the presence of hydrogen, i.e. reaction feeds with a CO 2 to H 2 ratio of 1:3, the surface chemistry at 300 K was very similar to that seen for pure CO 2 with the formation of ZnO x and carbonate groups. In contrast, at 500-600 K, reaction with hydrogen induced the removal of ZnO x and CO 3 /HCOO species. Finally, our AP-XPS results are consistent with the idea that CO 2 hydrogenation on AuZn alloys involves a redox process where there is sequential oxidation by CO 2 and reduction by H 2 to yield methanol.

36 MATERIALS SCIENCE↗