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DOE OSTI2014

Stem cell factor (SCF) protects osteoblasts from oxidative stress through activating c-Kit-Akt signaling

Highlights: • SCF receptor c-Kit is functionally expressed in primary and transformed osteoblasts. • SCF protects primary and transformed osteoblasts from H{sub 2}O{sub 2}. • SCF activation of c-Kit in osteoblasts, required for its cyto-protective effects. • c-Kit mediates SCF-induced Akt activation in cultured osteoblasts. • Akt activation is required for SCF-regulated cyto-protective effects in osteoblasts. - Abstract: Osteoblasts regulate bone formation and remodeling, and are main target cells of oxidative stress in the progression of osteonecrosis. The stem cell factor (SCF)-c-Kit pathway plays important roles in the proliferation, differentiation and survival in a range of cell types, but little is known about its functions in osteoblasts. In this study, we found that c-Kit is functionally expressed in both osteoblastic-like MC3T3-E1 cells and primary murine osteoblasts. Its ligand SCF exerted significant cyto-protective effects against hydrogen peroxide (H{sub 2}O{sub 2}). SCF activated its receptor c-Kit in osteoblasts, which was required for its cyto-protective effects against H{sub 2}O{sub 2}. Pharmacological inhibition (by Imatinib and Dasatinib) or shRNA-mediated knockdown of c-Kit thus inhibited SCF-mediated osteoblast protection. Further investigations showed that protection by SCF against H{sub 2}O{sub 2} was mediated via activation of c-Kit-dependent Akt pathway. Inhibition of Akt activation, through pharmacological or genetic means, suppressed SCF-mediated anti-H{sub 2}O{sub 2} activity in osteoblasts. In summary, we have identified a new SCF-c-Kit-Akt physiologic pathway that protects osteoblasts from H{sub 2}O{sub 2}-induced damages, and might minimize the risk of osteonecrosis caused by oxidative stress.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2015

At least 10% shorter C–H bonds in cryogenic protein crystal structures than in current AMBER forcefields

High resolution protein crystal structures resolved with X-ray diffraction data at cryogenic temperature are commonly used as experimental data to refine forcefields and evaluate protein folding simulations. However, it has been unclear hitherto whether the C–H bond lengths in cryogenic protein structures are significantly different from those defined in forcefields to affect protein folding simulations. This article reports the finding that the C–H bonds in high resolution cryogenic protein structures are 10–14% shorter than those defined in current AMBER forcefields, according to 3709 C–H bonds in the cryogenic protein structures with resolutions of 0.62–0.79 Å. Also, 20 all-atom, isothermal–isobaric, 0.5-μs molecular dynamics simulations showed that chignolin folded from a fully-extended backbone formation to the native β-hairpin conformation in the simulations using AMBER forcefield FF12SB at 300 K with an aggregated native state population including standard error of 10 ± 4%. However, the aggregated native state population with standard error reduced to 3 ± 2% in the same simulations except that C–H bonds were shortened by 10–14%. Furthermore, the aggregated native state populations with standard errors increased to 35 ± 3% and 26 ± 3% when using FF12MC, which is based on AMBER forcefield FF99, with and without the shortened C–H bonds, respectively. These results show that the 10–14% bond length differences can significantly affect protein folding simulations and suggest that re-parameterization of C–H bonds according to the cryogenic structures could improve the ability of a forcefield to fold proteins in molecular dynamics simulations. - Highlights: • Cryogenic crystal structures are commonly used in computational studies of proteins. • C–H bonds in the cryogenic structures are shorter than those defined in forcefields. • A survey of 3709 C–H bonds shows that the cryogenic bonds are 10–14% shorter. • The 10–14% differences affect molecular dynamics simulations of protein folding. • Shortening C–H bonds by 10–14% can improve protein folding simulations.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2016

Measurements of 14 C in ancient ice from Taylor Glacier, Antarctica constrain in situ cosmogenic 14 CH 4 and 14 CO production rates

Carbon-14 ( 14 C) is incorporated into glacial ice by trapping of atmospheric gases as well as direct near-surface in situ cosmogenic production. 14 C of trapped methane ( 14 CH 4 ) is a powerful tracer for past CH 4 emissions from “old” carbon sources such as permafrost and marine CH 4 clathrates. 14 C in trapped carbon dioxide ( 14 CO 2 ) can be used for absolute dating of ice cores. In situ produced cosmogenic 14 C in carbon monoxide ( 14 CO) can potentially be used to reconstruct the past cosmic ray flux and past solar activity. Unfortunately, the trapped atmospheric and in situ cosmogenic components of 14 C in glacial ice are difficult to disentangle and a thorough understanding of the in situ cosmogenic component is needed in order to extract useful information from ice core 14 C. Here, we analyzed very large (≈1000 kg) ice samples in the 2.26–19.53 m depth range from the ablation zone of Taylor Glacier, Antarctica, to study in situ cosmogenic production of 14 CH 4 and 14 CO. All sampled ice is >50 ka in age, allowing for the assumption that most of the measured 14 C originates from recent in situ cosmogenic production as ancient ice is brought to the surface via ablation. Our results place the first constraints on cosmogenic 14 CH 4 production rates and improve on prior estimates of 14 CO production rates in ice. We find a constant 14 CH 4 / 14 CO production ratio (0.0076 ± 0.0003) for samples deeper than 3 m, which allows the use of 14 CO for correcting the 14 CH 4 signals for the in situ cosmogenic component. Our results also provide the first unambiguous confirmation of 14 C production by fast muons in a natural setting (ice or rock) and suggest that the 14 C production rates in ice commonly used in the literature may be too high.

58 GEOSCIENCES↗

DOE OSTI2013

Enhanced visible light photocatalytic hydrogen evolution of sulfur-doped polymeric g-C{sub 3}N{sub 4} photocatalysts

Graphical abstract: - Highlights: • Sulfur-doped g-C{sub 3}N{sub 4} was prepared using thiourea as sulfur source. • The sulfur-doped g-C{sub 3}N{sub 4} shows significantly enhanced H{sub 2} evolution activity. • The doped sulfur species plays key roles in the improvement of H{sub 2} production. • Photocatalytic mechanism is proposed based on the experimental results. • The mechanism is confirmed by PL spectra and transient photocurrent curves. - Abstract: Visible light-activated sulfur-doped g-C{sub 3}N{sub 4} photocatalysts were successfully synthesized using thiourea as sulfur source. The obtained photocatalysts were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microcopy, ultraviolet–visible diffuse reflection spectroscopy, X-ray photoelectron spectroscopy, photoluminescence spectroscopy and transient photocurrent response. The sulfur-doped g-C{sub 3}N{sub 4} photocatalysts show beneficial effects on visible light absorption, electron–hole pair generation and separation. The sulfur species doped in the samples was identified as S{sup 2−} to replace N atoms in the g-C{sub 3}N{sub 4} framework. The photocatalytic activities of the sulfur-doped g-C{sub 3}N{sub 4} under visible light were evaluated by hydrogen evolution from water splitting in aqueous solution containing methanol. The sulfur-doped g-C{sub 3}N{sub 4} photocatalyst showed the highest photocatalytic performance with H{sub 2} evolution rate of 12.16 μmol h{sup −1}, about 6 times higher than un-doped g-C{sub 3}N{sub 4}. It can be concluded that the sulfur species play a vital role and act as active sites in the photocatalytic reaction. This novel sulfur-doped g-C{sub 3}N{sub 4} can be potentially used in energy and environmental applications.

36 MATERIALS SCIENCE↗

DOE OSTI2015

The physical properties of Li-doped g-C{sub 3}N{sub 4} monolayer sheet investigated by the first-principles

Highlights: • Systematically research on Li-doped g-C{sub 3}N{sub 4} monolayer sheets by first-principles calculation. • Optimal dopant concentration for optical absorption is 7.12%. • Thermodynamics stability of the doped substrate g-C{sub 3}N{sub 4} decreased with Li dopant concentration increasing. • The values of work function Φ decreased monotonously with the increasing of Li dopant concentration. - Abstract: The geometric, electronic, optical properties, thermodynamic stability, and work function of Li-doped g-C{sub 3}N{sub 4} monolayer were investigated by the first-principles calculation. It was found that the Li atoms were preferentially substituted the open-hollow sites of g-C{sub 3}N{sub 4}. Interestingly, the “odd” number of Li doped g-C{sub 3}N{sub 4} showed metallic properties, while the “even” number of Li atoms widened the band gap of g-C{sub 3}N{sub 4}. The HOMO and LUMO distributions reveal that the active sites located at edge N and C atoms for both pristine and the Li-doped g-C{sub 3}N{sub 4}. In addition, thermodynamic analysis showed that the doped Li atoms reduced the thermodynamic stability of g-C{sub 3}N{sub 4} monolayer sheets.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2016

Synergetic effect of MoS{sub 2} and g-C{sub 3}N{sub 4} as cocatalysts for enhanced photocatalytic H{sub 2} production activity of TiO{sub 2}

Highlights: • A hydrogen evolution reaction of g-C{sub 3}N{sub 4}/MoS{sub 2}/TiO{sub 2} photocatalyst was synthesized. • g-C{sub 3}N{sub 4}/MoS{sub 2}/TiO{sub 2} presents highly efficient H{sub 2} evolution without noble metals. • The effect of g-C{sub 3}N{sub 4} and MoS{sub 2} co-catalyst content in the composites was studied. • The mechanism of g-C{sub 3}N{sub 4}/MoS{sub 2}/TiO{sub 2} photocatalyst under UV–vis light was discussed. - Abstract: In this paper, we report a new g-C{sub 3}N{sub 4}/MoS{sub 2}/TiO{sub 2} composite material as a high-performance photocatalyst for H{sub 2} evolution. Without a noble-metal cocatalyst, the g-C{sub 3}N{sub 4}/MoS{sub 2}/TiO{sub 2} composite reaches a high H{sub 2} production rate of 125 μmol h{sup −1} when the content of the g-C{sub 3}N{sub 4}/MoS{sub 2} cocatalyst is 1.0 wt.% and the content of g-C{sub 3}N{sub 4} in this cocatalyst is 10 wt.%. This unusual photocatalytic activity is attributed to the positive synergetic effect between the MoS{sub 2} and g-C{sub 3}N{sub 4} components in this cocatalyst, which serve as an electron collector and a source of active adsorption sites, respectively.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Rain footprints on C-band synthetic aperture radar images of the ocean - Revisited

It is well known that rain leaves footprints on the sea surface that sometimes become visible on synthetic aperture radar (SAR) images. Rain cells can easily be detected on SAR images at all radar frequencies when they are associated with a downdraft pattern. But rain cells are not always associated with downdraft and rain can also occur in other forms, as stratified rain, rain bands, and squall lines. It turns out that radar signatures of rain at C-band are much more complex than at L- or X-band radar and that it is particularly difficult to identify unambiguously rain events on C-band SAR images acquired over the ocean. This is because C-band lies in the transition region where raindrops impinging onto the sea surface can increase (usually) or decrease the backscattered radar power and where volume scattering and attenuation by rain drops in the atmosphere are not always negligible (at very high rain rates). In order to get an insight into the physical mechanisms causing the C-band radar signatures of rain, we first revisit results obtained from historic laboratory and field experiments and multi-frequency/multi-polarization SAR data acquired during the SIR-C/X-SAR spaceshuttle mission in 1994. Then we analyze several C-band SAR images acquired by the European satellites Envisat and Sentinel-1A, and the Canadian satellite Radarsat-2 and compare them, whenever possible, with quasi-coincident and collocated weather radar images. The observational data show that, at low to medium rain rates, the main physical mechanism causing C-band radar signatures of rain is Bragg scattering at ring waves generated by the rain drops impinging onto the sea surface, which increase the radar backscatter. However, areas of increased radar backscatter are often accompanied by adjacent areas of decreased radar backscatter, which is due to attenuation of the Bragg waves by turbulence also generated by the impinging rain drops. Furthermore, we present a full-polarimetric Radarsat-2 SAR image of a rain cell together with a polarimetric decomposition analysis, which shows that the C-band radar signature of a rain cell is caused by surface scattering. The observation show that radar signatures of rain cells often contain segments, where the co-polarized as well the cross-polarized radar backscatter are strongly enhanced, which indicates non-Bragg scattering contributions to the scattering process. Furthermore, the polarimetric decomposition analysis shows that the C-band radar signature of a rain cell is dominated by surface scattering. Possible mechanisms, like scattering at splash products, are discussed. Whether the normalized radar cross section (NRCS) due to rain is increased or decreased depends on rain rate, wind speed, incidence angle, and history of the rain event. At low to moderate wind speeds (< 10 ms - 1 ) and low to medium high rain rates (< 50 mm h - 1 ), the NRCS is usually increased by up to 8 dB, and at high wind speeds (> 10 m s - 1 ) and low to high rain rates (but < 50 mm h - 1 ), the NRCS is usually decreased by up to 3 dB.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2017

Prediction of thyroid C-cell carcinogenicity after chronic administration of GLP1-R agonists in rodents

Increased incidence of C-cell carcinogenicity has been observed for glucagon-like-protein-1 receptor (GLP-1r) agonists in rodents. It is suggested that the duration of exposure is an indicator of carcinogenic potential in rodents of the different products on the market. Furthermore, the role of GLP-1-related mechanisms in the induction of C-cell carcinogenicity has gained increased attention by regulatory agencies. This study proposes an integrative pharmacokinetic/pharmacodynamic (PKPD) framework to identify explanatory factors and characterize differences in carcinogenic potential of the GLP-1r agonist products. PK models for four products (exenatide QW (once weekly), exenatide BID (twice daily), liraglutide and lixisenatide) were developed using nonlinear mixed effects modelling. Predicted exposure was subsequently linked to GLP-1r stimulation using in vitro GLP-1r potency data. A logistic regression model was then applied to exenatide QW and liraglutide data to assess the relationship between GLP-1r stimulation and thyroid C-cell hyperplasia incidence as pre-neoplastic predictor of a carcinogenic response. The model showed a significant association between predicted GLP-1r stimulation and C-cell hyperplasia after 2 years of treatment. The predictive performance of the model was evaluated using lixisenatide, for which hyperplasia data were accurately described during the validation step. The use of a model-based approach provided insight into the relationship between C-cell hyperplasia and GLP-1r stimulation for all four products, which is not possible with traditional data analysis methods. It can be concluded that both pharmacokinetics (exposure) and pharmacodynamics (potency for GLP-1r) factors determine C-cell hyperplasia incidence in rodents. Our work highlights the pharmacological basis for GLP-1r agonist-induced C-cell carcinogenicity. The concept is promising for application to other drug classes. - Highlights: • An integrative PKPD model is applied to study GLP-1r agonist carcinogenicity. • C-cell carcinogenicity is impacted by both pharmacokinetics and pharmacodynamics. • The relation of GLP-1r stimulation and C-cell hyperplasia appears drug-independent. • Understanding carcinogenic risk needs a pharmacological basis.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2023

Engineering bimetallic interfaces and revealing the mechanism for carbon dioxide electroreduction to C 3+ liquid chemicals

Reduction reaction of CO 2 (CO 2 RR) to liquid C 3+ chemicals is a net-zero-carbon process and can increase local resiliency to power outages and fuel consumption. The mechanism and the catalyst design rules of CO 2 RR-to-C 3+ are unknown. Engineering bimetallic interface (e.g., Pd/Au) to tune the intermediate adsorption is promising for promoting C 3+ formation. Our density functional theory (DFT) calculations find that *CH 2 could be the key intermediate and C 1 -CH 2 coupling could be the rate-limiting step to generate C 3+ . High CO surface coverages can promote the bimetallic interfacial sites, lower the energetics of the C 1 -CH 2 coupling step, and enhance the C 3+ formation. We further construct a volcano plot of C 1 -CH 2 kinetics as a function of the binding strength of key intermediate *CH 2 via engineering the d-band center of the interfacial site. Our findings could guide the rational design of bimetallic interfaces and their near-surface microenvironment for enhancing CO 2 RR-to-C 3+ .

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2021

High-Pressure Synthesis of Bulk Cobalt Cementite, Co 3 C

Transition metal carbides find use in a wide range of advanced high-resilience applications including high-strength steels, heat shields, and deep-earth drills. However, carbides of the mid-to-late transition metals remain difficult to isolate and characterize on account of their metastability, which precludes the preparation of high-quality bulk single crystal samples using traditional solid-state methods. Herein, we report a combined computational and experimental survey of the cobalt-carbon binary system under high pressures and demonstrate that pressure offers a route toward the bulk synthesis of the metastable cementite-type cobalt carbide, Co 3 C, which under ambient conditions can only be prepared in low-dimensional thin film or nanoparticle forms. First-principles calculations reveal two competitive low-energy stoichiometric phases under ambient pressures - Pnnm-Co 2 C (Fe 2 C-type) and Pnma-Co 3 C (Fe 3 Ctype) - consistent with the known low-dimensional phases that have been studied for their promising magnetic properties. However, the calculated formation enthalpy of Pnma-Co 3 C decreases steadily with the applied pressure, while that of Pnnm-Co 2 C increases. Here, we pursue these results using high-pressure laser-heated synthesis methods coupled with in situ X-ray diffraction and observe the formation of Pnma-Co 3 C above 4.8 GPa. We determine the experimental bulk modulus of Co 3 C to be K o = 237 GPa (K p = 4.0). First-principles calculations of the phonon modes in Co 3 C reveal dynamical instabilities at ambient pressure that are absent under compression. These results offer a promising new route for the synthesis of rare-earth-free magnets.

36 MATERIALS SCIENCE↗

DOE OSTI2025

The [M 6 (S 2 C 2 Ph 2 ) 6 ] (M = Ni, Pd, Pt) Series: Multielectron Reservoirs That Sustain Ligand-Based Oxidations and Metal-Based Reductions

A complete [M 6 (S 2 C 2 R 2 ) 6 ] series (M = Ni (1), Pd (2), Pt (3); R = Ph), the rarest variety among homoleptic dithiolene transition-metal compounds, has been prepared by reaction between [M(S 2 C 2 Ph 2 ) 2 ] and a M 0 source. The platinum member of this set is the first of its type. Diffraction-quality crystals, grown with high reproducibility by evaporation from PhNO 2 solutions, reveal fully reduced [Ph 2 C 2 S 2 ] 2– dianions and an octahedral M 6 core that is reduced to C 2 symmetry by the fusion of a mononuclear D 2h [M(S 2 C 2 Ph 2 ) 2 ] fragment upon a C 4 -symmetric base. The [Ni 6 (S 2 C 2 Ph 2 ) 2 ] 1– monoanion, prepared by Cp* 2 Co reduction, shows only modest structural differences from its neutral counterpart. In CH 2 Cl 2 , 1 and 2 can undergo two reductions and an oxidation, while 3 sustains two reductions and two oxidations. In benzonitrile, 1 sustains three reversible oxidations at potentials that are shifted appreciably to less positive values. The cathodic processes are shown by density functional theory (DFT) calculations to involve an MO largely of metal–sulfur composition that has contributions throughout the C 4 -symmetric pentametallic base of the assembly, while the oxidations are largely ligand-based and confined to the monometallic [M(S 2 C 2 Ph 2 ) 2 ] cap. The absorption spectra are marked by multiple overlapping bands that produce a continuous, tapering absorption profile of unresolved shoulders and swells.

Ligands↗

DOE OSTI2023

Reactivity and Mechanisms of Methane, Ethane, and Benzene C–H Amination with an Iodine(III) Bistriflimide Complex

The iodine(III) bistriflamide complex (C 6 F 5 ) III I(NTf 2 ) 2 in HNTf 2 (bistriflimide acid; (CF 3 SO 2 ) 2 NH) selectively aminates methane and ethane. At a 100 °C reaction with methane after 3 h, it resulted in the exclusive formation of MeNTf 2 with a yield of approximately 40%. For ethane, at 100 °C in 2 h, a > 80% yield was found for a combination of monofunctionalized and difunctionalized amination products. In contrast to alkanes giving functionalized products, the reaction of (C 6 F 5 ) III I(NTf 2 ) 2 with benzene resulted in being stalled at (C 6 F 5 )I III (Ph)(NTf 2 ) with a <5% conversion to PhNTf 2 even at 120 °C. PWPB95-D3(BJ) density functional theory calculations indicate that C–H activation is the lowest energy pathway to break the hydrocarbon bonds and is lower in energy than radical, electron-transfer, proton-coupled electron-transfer, or hydride substitution pathways. For methane, from the (C 6 F 5 )I III (CH 3 )(NTf 2 ) intermediate, there is a one-step amine functionalization mechanism that avoids a carbocation intermediate. For ethane, from the (C 6 F 5 )I III (Et)(NTf 2 ) intermediate, dynamics simulations suggest the possibility of a competitive two-step functionalization pathway that involves a short-lived carbocation intermediate. As a result, a reaction coordinate strain analysis provides a straightforward model for understanding the relative reactivity rates for alkyl versus aryl functionalization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Monolayer Ti 3 C 2 T x as an Effective Co-catalyst for Enhanced Photocatalytic Hydrogen Production over TiO 2

Titanium dioxide (TiO 2 ) represents a promising candidate for hydrogen production via photocatalysis. Yet, its large bandgap and fast charge recombination limits its efficiency. To overcome this limitation, we explored in this work two-dimensional titanium carbide MXene, Ti 3 C 2 T x ( T x = O, OH, F), as feasible co-catalysts for hydrogen production with TiO 2 as the photocatalyst. We synthesized a series of Ti 3 C 2 T x /TiO 2 composite photocatalysts with monolayer Ti 3 C 2 T x as the co-catalyst to improve the separation of photoinduced electrons and holes. The physicochemical properties of the Ti 3 C 2 T x /TiO 2 composites were investigated by a variety of characterization techniques, and the effect of the monolayer Ti 3 C 2 T x on the photocatalytic performance of the Ti 3 C 2 T x /TiO 2 composites is elucidated by comparison to the multilayer counterpart. The photocatalytic hydrogen evolution rate of the optimized monolayer Ti 3 C 2 T x /TiO 2 composite is over 9 times higher than that of the pure TiO 2 and 2.5 times higher than the multilayer counterpart. The significantly enhanced activity is attributed to the superior electrical conductivity of monolayer Ti 3 C 2 T x and charge-carrier separation at the MXene/TiO 2 interface. A mechanism of photocatalytic hydrogen evolution over the Ti 3 C 2 T x /TiO 2 system is proposed. Our work reports on the potential of monolayer MXenes as effective co-catalysts for photocatalysis and further broadens the applications of the MXene family of two-dimensional materials.

08 HYDROGEN↗

DOE OSTI2019

Diverse Mycorrhizal Associations Enhance Terrestrial C Storage in a Global Model

Accurate projections of the terrestrial carbon (C) sink are critical to understanding the future global C cycle and setting CO 2 emission reduction goals. Current earth system models (ESMs) and dynamic global vegetation models (DGVMs) with coupled carbon-nitrogen cycles project that future terrestrial C sequestration will be limited by nitrogen (N) availability, but the magnitude of N limitation remains a critical uncertainty. Plants use multiple symbiotic nutrient acquisition strategies to mitigate N limitation, but current DGVMs omit these mechanisms. Fully coupling N-acquiring plant-microbe symbioses to soil organic matter (SOM) cycling within a DGVM for the first time, we demonstrate that increases in N acquisition via SOM decomposition and atmospheric N 2 fixation could support long-term enhancement of terrestrial C sequestration at global scales under elevated CO 2 . The model reproduced elevated CO2 responses from two experiments (Duke and Oak Ridge) representing contrasting N acquisition strategies. N release from enhanced SOM decomposition supported vegetation growth at Duke, while inorganic N depletion limited growth at Oak Ridge. Global simulations reproduced spatial patterns of N-acquiring symbioses from a novel niche-based map of mycorrhizal fungi. Under a 100-ppm increase in CO2 concentrations, shifts in N acquisition pathways facilitated 200 Pg C of terrestrial C sequestration over 100 years compared to 50 Pg C for a scenario with static N acquisition pathways. Our results imply that N acquisition strategies are important determinants of terrestrial C sequestration potential under elevated CO 2 and that nitrogen-enabled DGVMs that omit symbiotic N acquisition may underestimate future terrestrial C uptake.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

pH effects on the electrochemical reduction of CO (2) towards C 2 products on stepped copper

Here, we present a microkinetic model for CO (2) reduction (CO (2) R) on Cu(211) towards C 2 products, based on energetics estimated from an explicit solvent model. We show that the differences in both Tafel slopes and pH dependence for C 1 vs C 2 activity arise from differences in their multi-step mechanisms. We find the depletion in C 2 products observed at high overpotential and high pH to arise from the 2nd order dependence of C-C coupling on CO coverage, which decreases due to competition from the C 1 pathway. We further demonstrate that CO (2) reduction at a fixed pH yield similar activities, due to the facile kinetics for CO 2 reduction to CO on Cu, which suggests C 2 products to be favored for CO 2 R under alkaline conditions. The mechanistic insights of this work elucidate how reaction conditions can lead to significant enhancements in selectivity and activity towards higher value C 2 products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

A charged diatomic triple-bonded U≡N species trapped in C 82 fullerene cages

Actinide diatomic molecules are ideal models to study elusive actinide multiple bonds, but most of these diatomic molecules have so far only been studied in solid inert gas matrices. Herein, we report a charged U≡N diatomic species captured in fullerene cages and stabilized by the U-fullerene coordination interaction. Two diatomic clusterfullerenes, viz. UN@C s (6)-C 82 and UN@C 2 (5)-C 82 , were successfully synthesized and characterized. Crystallographic analysis reveals U-N bond lengths of 1.760(7) and 1.760(20) Å in UN@C s (6)-C 82 and UN@C 2 (5)-C 82 . Moreover, U≡N was found to be immobilized and coordinated to the fullerene cages at 100 K but it rotates inside the cage at 273 K. Quantum-chemical calculations show a (UN) 2+ @(C 82 ) 2- electronic structure with formal +5 oxidation state (f 1 ) of U and unambiguously demonstrate the presence of a U≡N bond in the clusterfullerenes. This study constitutes an approach to stabilize fundamentally important actinide multiply bonded species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Two-dimensional hexagonal M 3 C 2 (M = Zn, Cd and Hg) monolayers: novel quantum spin Hall insulators and Dirac cone materials

The intriguing Dirac cones in honeycomb graphene have motivated the search for novel two-dimensional (2D) Dirac materials. Based on density functional theory and the global particle-swarm optimization method, herein, we predict a new family of 2D materials in honeycomb transition-metal carbides M 3 C 2 (M = Zn, Cd and Hg) with intrinsic Dirac cones. The M 3 C 2 monolayer is a kinetically stable state with a linear geometry (C=M=C), which to date has not been observed in other transition-metal-based 2D materials. The intrinsic Dirac cones in the Zn 3 C 2 , Cd 3 C 2 and Hg 3 C 2 monolayers arise from p–d band hybridizations. Importantly, the Hg 3 C 2 monolayer is a room-temperature 2D topological insulator with a sizable energy gap of 44.3 meV. When an external strain is applied, additional phases with node-line semimetal states emerge in the M 3 C 2 monolayer. These novel stable transition-metal–carbon-framework materials hold great promise for 2D electronic device applications.

Material Science↗

DOE OSTI2021

Planar defect-driven electrocatalysis of CO 2 -to-C 2 H 4 conversion

The selectivity towards a specific C 2+ product, such as ethylene (C 2 H 4 ), is sensitive to the surface structure of copper (Cu) catalysts in carbon dioxide (CO 2 ) electro-reduction. The fundamental understanding of such sensitivity can guide the development of advanced electrocatalysts, although it remains challenging at the atomic level. In this work, we demonstrated that planar defects, such as stacking faults, could drive the electrocatalysis of CO 2 -to-C 2 H 4 conversion with higher selectivity and productivity than Cu(100) facets in the intermediate potential region (–0.50 ~ –0.65 V vs. RHE). The unique right bipyramidal Cu nanocrystals containing a combination of (100) facets and a set of parallel planar defects delivered 67% faradaic efficiency (FE) for C 2 H 4 and a partial current density of 217 mA cm –2 at –0.63 V vs. RHE. In contrast, Cu nanocubes with exclusive (100) facets exhibited only 46% FE for C 2 H 4 and a partial current density of 87 mA cm –2 at an identical potential. Both ex situ CO temperature-programmed desorption and in situ Raman spectroscopy analysis implied that the stronger *CO adsorption on planar defect sites facilitates CO generation kinetics, which contributes to a higher surface coverage of *CO and in turn an enhanced reaction rate of C–C coupling towards C 2+ products, especially C 2 H 4 .

36 MATERIALS SCIENCE↗