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At least 343 records · Page 19

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DOE OSTI2024

A Ce-CuZn catalyst with abundant Cu/Zn-OV-Ce active sites for CO 2 hydrogenation to methanol

CO 2 hydrogenation to chemicals and fuels is a significant approach for achieving carbon neutrality. It is essential to rationally design the chemical structure and catalytic active sites towards the development of efficient catalysts. Here we show a Ce-CuZn catalyst with enriched Cu/Zn-OV-Ce active sites fabricated through the atomic-level substitution of Cu and Zn into Ce-MOF precursor. The Ce-CuZn catalyst exhibits a high methanol selectivity of 71.1% and a space-time yield of methanol up to 400.3 g·kg cat -1 ·h -1 with excellent stability for 170 h at 260°C, comparable to that of the state-of-the-art CuZnAl catalysts. Controlled experiments and DFT calculations confirm that the incorporation of Cu and Zn into CeO 2 with abundant oxygen vacancies can facilitate H 2 dissociation energetically and thus improve CO 2 hydrogenation over the Ce-CuZn catalyst via formate intermediates. This work offers an atomic-level design strategy for constructing efficient multi-metal catalysts for methanol synthesis through precise control of active sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Ultrathin Plasmonic Tungsten Oxide Quantum Wells with Controllable Free Carrier Densities

Localized surface plasmon resonances (LSPR) of nanostructures can be tuned by controlling their morphology, local dielectric environment, and free carrier concentration. We report the colloidal synthesis of an ~3 tungsten–oxygen (W-O) layer thick (~1 nm), two-dimensional (2D) WO 3-x nanoplatelets (NPLs) (x ≈ 0.55–1.03), which display tunable near-infrared LSPR properties and additionally high free electron density (N e ) that arises predominantly from the large shape factor of 2D NPLs. Importantly, the W to O composition ratios inferred from their LSPR measurements show much higher percentage of oxygen vacancies than those determined by X-ray diffraction analysis, suggesting that the aspect ratio of ultrathin WO 3-x NPLs is the key to producing an unprecedentedly large Ne, although synthesis temperature is also an independent factor. We find that NPL formation is kinetically controlled, whereas thermodynamic parameter manipulation leads to N e values as high as 4.13 × 10 22 cm –3 , which is close to that of plasmonic noble metals, and thus our oxide-based nanostructures can be considered as quasi-metallic. The unique structural properties of 2D nanomaterials along with the high N e of WO 3-x NPLs provide an attractive alternative to plasmonic noble metal nanostructures for various plasmon-driven energy conversions and design of photochromic nanodevices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Solute segregation and precipitation across damage rates in dual-ion–irradiated T91 steel

We report that dual-ion irradiations using 5.0 MeV defocused Fe 2+ ions and co-injected energy degraded 2.00 to 2.85 MeV He 2+ ions were conducted on a Fe9CrMo ferritic-martensitic steel T91 to 17 dpa at a damage rate range of 5 × 10 -5 dpa/s to 3 × 10 -3 dpa/s at 445°C, followed by characterization of the microstructure using conventional and scanning transmission electron microscopy. Radiation induced Ni/Si clusters and radiation induced segregation were quantified using energy dispersive X-ray spectroscopy at each condition and were compared with the same material irradiated in the BOR-60 reactor and in the as-received condition. No significant Cr segregation was found at lath boundaries after dual-ion irradiation, while Ni and Si enrichments both decreased with increasing damage rate leading to a sharp decrease in the density of Ni/Si clusters with damage rate. Increased point defect recombination at higher ion damage rates likely reduced the Ni/Si cluster density compared with BOR-60. Although the overall vacancy concentration and diffusion are enhanced by the irradiation damage rate, the lack of time for thermal diffusion and ballistic displacements of solutes are significant limiting factors for Ni/Si cluster formation. This work demonstrates the effect of irradiation damage rate on elemental segregation and clustering when using ion irradiation to simulate reactor irradiation.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Millisecond Conversion of Metastable 2D Materials by Flash Joule Heating

Controllable phase engineering is vital for precisely tailoring material properties since different phase structures have various electronic states and atomic arrangements. Rapid synthesis of thermodynamically metastable materials, especially two-dimensional metastable materials, with high efficiency and low cost remains a large challenge. Here we report flash Joule heating (FJH) as an electrothermal method to achieve the bulk conversion of transition metal dichalcogenides, MoS 2 and WS 2 , from 2H phases to 1T phases in milliseconds. The conversions can reach up to 76% of flash MoS 2 using tungsten powder as conductive additive. Different degrees of phase conversion can be realized by controlling the FJH conditions, such as reaction duration and additives, which allows the study of ratio-dependent properties. First-principles calculations confirm that structural processes associated with the FJH, such as vacancy formation and charge accumulation, result in stabilization of the 1T phases. Furthermore, FJH offers rapid access to bulk quantities of the hitherto hard-to-access 1T phases, a promising method for further fundamental research and diverse applications of metastable phases.

2D materials↗

DOE OSTI2025

Meso-scale modeling of UO2 nuclear fuel to high burnup

To improve the economics of light water reactors for commercial nuclear energy generation, utility operators are seeking to obtain regulatory approval to run UO2 fuel to higher levels of burnup. One potential impediment to obtaining this approval is the phenomenon of fuel fragmentation, relocation, and dispersal (FFRD). FFRD can result when fuel experiences a rapid temperature transient, such as that occurring during a Loss Of Coolant Accident (LOCA). FFRD has historically been most associated with the rim region in UO2 fuel pellets, where the phenomenon of fragmentation is also referred to as pulverization due to the small size of the fragments. More recent evidence suggests that the so-called “dark zone” (due to its appearance in micrographs) that can be observed in the mid-radial regions of high burnup fuel is also susceptible to FFRD. Although empirical fuel performance models have been developed that can adequately predict pulverization in the rim region under typical LWR conditions, a scientific understanding of what underlies fuel restructuring and subsequent FFRD is lacking even in the rim region, and no models are currently available for the behavior the dark zone. To address these challenges, the U.S. Department of Energy’s Nuclear Energy Advanced Modeling and Simulation (NEAMS) program has employed a multi-scale modeling approach to improve scientific understanding and develop new fuel performance models. In this talk, I will focus on meso-scale efforts, which form a crucial link between atomic-scale and engineering-scale models. Phase-field modeling combined with cluster dynamics is used to predict the restructuring process in the rim region. Phase-field fracture modeling, informed by atomistic simulations, is used to predict the onset of pulverization in the rim region. Combining these techniques together allows the extent of rim pulverization to be predicted. The formation and evolution of the dark zone has also been simulated with the phase-field method, using an improved approach to vacancy source term parameterization. The work shows the important impact of microstructure on fuel performance.

fracture↗

NASA NTRS1996

Crystallography of the NiHfSi Phase in a NiAl (0.5 Hf) Single-Crystal Alloy

Small additions of Hf to conventionally processed NiAl single crystals result in the precipitation of a high density of cuboidal G-phase along with a newly identified silicide phase. Both of these phases form in the presence of Si which is not an intentional alloying addition but is a contaminant resulting from contact with the ceramic shell molds during directional solidification of the single-crystal ingots. The morphology, crystal structure and Orientation Relationship (OR) of the silicide phase in a NiAl (0.5 at.%Hf) single-crystal alloy have been determined using transmission electron microscopy, electron microdiffraction and energy dispersive X-ray spectroscopy. Qualitative elemental analysis and indexing of the electron microdiffraction patterns from the new phase indicate that it is an orthorhombic NiHfSi phase with unit cell parameters, a = 0.639 nm, b = 0.389 nm and c = 0.72 nm, and space group Pnma. The NiHfSi phase forms as thin rectangular plates on NiAl/111/ planes with an OR that is given by NiHfSi(100))(parallel) NiAl(111) and NiHfSi zone axes(010) (parallel) NiAl zone axes (101). Twelve variants of the NiHfSi phase were observed in the alloy and the number of variants and rectangular morphology of NiHfSi plates are consistent with symmetry requirements. Quenching experiments indicate that nucleation of the NiHfSi phase in NiAI(Hf) alloys is aided by the formation of NiAl group of zone axes (111) vacancy loops that form on the NiAl /111/ planes.

Garg, A.↗

DOE OSTI2024

Phase stability and microstructure of neutron-irradiated substoichiometric yttrium dihydrides

The impact of the neutron-displacement damage on phase stability and microstructure of substoichiometric yttrium dihydrides (YH x , x <2) were investigated to assess their use as solid moderator in high-temperature nuclear reactors. YH x specimens were, thus, subjected to neutron irradiations in the range of 0.1–2 displacements per yttrium atom (dpa-Y) in the temperature range of 536–878°C at the Oak Ridge National Laboratory's (ORNL's) High Flux Isotope Reactor (HFIR). YH x specimens were initially prepared at stoichiometry (H/Y) ratios of 1.69 and 1.83. HFIR-irradiated specimens were characterized by variety of techniques to investigate H retention characteristics including dimensional analysis, optical microscopy, scanning electron microscopy electron back scatter diffraction (EBSD), transmission electron microscopy, thermal desorption spectroscopy (TDS), and high-energy x-ray diffraction (HE-XRD) characterizations. Overall, YH x exhibited notable structural and phase stability under short-term neutron-irradiation, except for the samples with significant silicon carbide (SiC) interaction at high doses and temperatures. Basic dimensional and mass measurements were misleading for accurate assessment of H retention, as confirmed by EBSD phase maps, XRD line profiles, and TDS signals. Thus, it was discussed that a robust H retention metric is needed to assess irradiated hydrides. Further, nanoscale cavities were observed as a result of the neutron irradiation in all samples. Although no clear impact of dose and irradiation temperature was determined, the initial H/Y ratio had an impact on the cavity number density where low H/Y specimens had high-resistance to cavity formation. The Y-vacancy cluster formation at the collision stage of the displacement cascade and their stabilization by H were considered to be the likely underlying mechanisms for the observed cavity microstructure.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

DOE OSTI2026

Thermodynamics of Tritium Trapping by Point Defects at Interfacial Cr-based Phases of the Al Coating

Density functional theory (DFT) simulations have been carried out to evaluate the potential for tritium trapping by metal vacancies in four phases Cr-containing phases (i.e., Cr3Si, Al0.3Cr0.7, Al8Cr5-HT, and Al8Cr5) identified near the interface between the Al coating and 316 stainless steel (316 SS) cladding. In addition, an ab initio thermodynamics approach has been employed to predict the temperature and T2-partial pressure dependence on the thermodynamics of singly tritiated defects. Key results in this work suggest that metal vacancies in the four phases have the potential to favorably trap tritium species, especially Si vacancies in Cr3Si phase. This overall thermodynamic trend can be correlated to the energy cost of having an interstitial tritium in the lattice, which has been calculated to range from 0.17 eV in Al8Cr5-HT to 0.89 eV in Cr3Si. A comparison of the results from this study with previous theoretical works investigating tritium behavior in other Fe-Al phases identified in the aluminide coating, suggests that metal vacancies are generally able to trap tritium in various Fe-Al aluminide phases. Especially, it was found that Si and Al vacancies would be the most efficient to trap for tritium, followed by Cr vacancies, then Fe and Ni vacancies. In the four Cr-based material phases investigated in this work, it is interesting to note that, in the absences of Fe or Ni species, strong interactions between tritium and the metal vacancies are always occurring by the formation of preferential Cr—T bonds (i.e., no Si—T or Al—T bonds were formed).

Sassi, Michel J.↗

DOE OSTI2023

Redox Chemistry of the Subphases of α-CsPbI2Br and β-CsPbI2Br: Theory Reveals New Potential for Photostability

The logic in the design of a halide-mixed APb(I 1-x Br x ) 3 perovskite is quite straightforward: to combine the superior photovoltaic qualities of iodine-based perovskites with the increased stability of bromine-based perovskites. However, even small amounts of Br doped into the iodine-based materials leads to some instability. In the present report, using first-principles computations, we analyzed a wide variety of α-CsPbI 2 Br and β-CsPbI 2 Br phases, compared their mixing enthalpies, explored their oxidative properties, and calculated their hole-coupled and hole-free charged Frenkel defect (CFD) formations by considering all possible channels of oxidation. Nanoinclusions of bromine-rich phases in α-CsPbI 2 Br were shown to destabilize the material by inducing lattice strain, making it more susceptible to oxidation. The uniformly mixed phase of α-CsPbI 2 Br was shown to be highly susceptible towards a phase transformation into β-CsPbI 2 Br when halide interstitial or halide vacancy defects were introduced into the lattice. The rotation of PbI 4 Br 2 octahedra in α-CsPbI2Br allows it either to transform into a highly unstable apical β-CsPbI 2 Br, which may phase-segregate and is susceptible to CFD, or to phase-transform into equatorial β-CsPbI 2 Br, which is resilient against the deleterious effects of hole oxidation (energies of oxidation >0 eV) and demixing (energy of mixing <0 eV). Thus, the selective preparation of equatorial β-CsPbI 2 Br offers an opportunity to obtain a mixed perovskite material with enhanced photostability and an intermediate bandgap between its constituent perovskites.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Tritium diffusion and formation in the bulk and defective surface of γ-LiAlO2 pellets: First-principles investigation

In tritium-producing burnable absorber rods (TPBAR), γ-LiAlO2 is used in the form of an annular ceramic pellet enriched with the 6Li isotope. When irradiated in a pressurized water reactor (PWR), the 6Li pellets absorb neutrons and produce tritium (3H) through 6Li + n 3H + α. The 3H chemically reacts with the metal getter where it is captured and leads to formation of a metal hydride. For TPBARs to enable effective tritium production in PWRs, we investigated the 3H diffusion pathways in the bulk and surface of γ-LiAlO2 with different concentrations of lithium defects. The calculated results for bulk and low-index surfaces, thermal conductivity, 3H activation energy barriers, and the 3H diffusion coefficients in γ-LiAlO2 are in good agreement with the available experimental values. In the bulk, our results show that the smallest activation energy barrier is 0.63 eV for substitutional 3H diffusion with a diffusion coefficient of 3.25x10-12 m2/s. After 3H diffused from bulk to the surface, it could form different species (such as 3H2, 3H2O, C3H4) depending on the surface structure, vacancy types and the impurity carbon. Our results indicate that the 3H2 is the main product from γ-LiAlO2 pellets. As the number of VLi vacancies and 3H atoms increases under irradiation (3H-rich condition), 3H2O release could increase from the surface of γ-LiAlO2 pellets.

Jia, Ting↗

DOE OSTI2022

Visible Light Absorption and Hot Carrier Trapping in Anatase TiO 2 : The Role of Surface Oxygen Vacancies

Anatase TiO 2 is an efficient water splitting photocatalyst using UV light, but solar energy harvesting requires the presence of midgap states to increase visible light absorption. Despite numerous studies, important questions remain regarding the photophysics in O vacancy doped TiO 2 . Here, by employing extreme ultraviolet reflection–absorption (XUV-RA) spectroscopy at the Ti M2,3-edge, spectral signatures of both large and small polaron states are identified, allowing ultrafast electron and hole dynamics in these states to be independently resolved. Results show that visible light absorption occurs via promotion of an electron from the small polaron state to the TiO 2 conduction band. In contrast, absorption of UV light results in direct band gap excitation followed by carrier relaxation during which hot holes trap as small polarons in 45 ± 42 fs, and hot electrons couple to polar optical phonons leading to vibrational coherence and large polaron formation in 945 ± 92 fs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Mechanistic understanding of support effect on the activity and selectivity of indium oxide catalysts for CO 2 hydrogenation

Herein we present a mechanistic study on the support effect (ZrO 2 and CeO 2 ) of In 2 O 3 catalysts in CO 2 hydrogenation by a combined experimental and computational approach. Kinetic experiments and surface characterization suggested that the activity of In 2 O 3 catalysts cannot be simply correlated with the abundance of surface oxygen vacancies (O v ) formed by either H 2 -reduction or thermal treatment, which has been frequently invoked in previous studies. The support effect should originate from the electronic interactions between In 2 O 3 and the support oxide, rather than geometric factors or the difference in the particle size of In 2 O 3 . Theoretical modelling revealed that surface O v facilitate the formation and stabilization of the formate (HCOO*) intermediate. While a carbonate-like structure is favored for CO 2 adsorption on CeO 2 -supported or unsupported In 2 O 3 catalysts, CO 2 tends to bind strongly in a bent configuration on the O v site at the In 2 O 3 -ZrO 2 interface. The distinct CO 2 adsorption structures on different supported In 2 O 3 catalysts may account for the different reaction energy profiles in the subsequent hydrogenation reactions, especially the rate-limiting step, i.e., hydrogenation of HCOO* to CH 2 O* and methoxy (CH 3 O*). The relatively higher methanol selectivity of In 2 O 3 catalyst supported on ZrO 2 with respect to that on CeO 2 are suggested to stem from the greater energy difference (Δ$E_a$) between the parallel hydrogenation and C-O bond cleavage of HCOO*, which leads to the formation of methanol and CO, respectively. We report this study underlines the important role of metal-oxide-interface in determining the catalytic behavior of oxide-supported In 2 O 3 catalysts in CO 2 conversion.

30 DIRECT ENERGY CONVERSION↗

DOE OSTI2021

Ligand-Free Processable Perovskite Semiconductor Ink

We report traditional covalent semiconductors require complex processing methods for device fabrication due to their high cohesive energies. Here, we develop a stable, ligand-free perovskite semiconductor ink that can be used to make patterned semiconductor-based optoelectronics in one step. The perovskite ink is formed via the dissolution of crystals of vacancy-ordered double perovskite Cs 2 TeX 6 (X = Cl - , Br - , I - ) in polar aprotic solvents, leading to the stabilization of isolated [TeX 6 ] 2- octahedral anions and free Cs + cations without the presence of ligands. The stabilization of the fundamental perovskite ionic octahedral building blocks in solution creates multifunctional inks with the ability to reversibly transform between the liquid ink and the solid-state perovskite crystalline system in air within minutes. These easily processable inks can be patterned onto various materials via dropcasting, spraying or painting, and stamping, highlighting the crucial role of solvated octahedral complexes toward the rapid formation of phase-pure perovskite structures in ambient conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Mechanistic Insights for Plasma-Catalytic CO 2 Reduction over TiO 2 in a Dielectric Barrier Discharge Reactor

Reaction kinetics experiments coupled with phenomenological kinetic modeling and parameter estimation are used to elicit insights into the mechanism and active sites for the plasma-catalytic dissociation of CO 2 on TiO 2 . Experimental and model insights showed that gas-phase reactions contribute at least two-thirds of the overall product formation at explored conditions; weak temperature dependence, strong sensitivity to specific energy input (SEI), apparent first order in CO 2 , and positive influence of cofed argon (Ar) and oxygen (O 2 ) for the gas-phase contributions all suggest that expected plasma reaction steps such as electron-impact and high-energy collisions are the dominant modes for CO 2 dissociation. The Arrhenius-like expression for gas contributions resulted in a preexponential of 4.40 × 10 –3 s –1 , an E SEI,g of 7.90 × 10 –4 mol/kJ, and an E a,g of 1.00 × 10 –3 J/mol. For surface contributions, the small apparent barrier of 16.3 kJ/mol, relatively weaker dependence on SEI, first-order dependence on CO 2 , and insensitivity to cofed Ar and O 2 all point to CO 2 dissociation on TiO 2 surface facets without vacancies and aided by plasma (leading to vibrationally excited CO 2 and/or a reactive surface with significant surface charge accumulation). The Arrhenius-like expression resulted in a preexponential of 7.81 × 10 –2 s –1 , an E SEI,s of 1.90 × 10 –3 mol/kJ, and an E a,s of 1.63 × 10 4 J/mol. The derived kinetic model further enabled a systematic evaluation of the effect of inputs (plasma power, flow rate, CO 2 inlet concentration, and temperature) to identify process trends and optimal operating conditions.

catalyst↗

DOE OSTI2025

Strain-driven oxygen vacancy ordering in LaNiO 3 thin films revealed by integrated differential phase contrast imaging in scanning transmission electron microscopy

Rare-earth nickelates, such as LaNiO 3 (LNO), exhibit complex electronic properties, with ordered oxygen vacancies (OOV) influencing conductivity and magnetic behavior. We investigate the structural stability of strain-induced OOV phases in LNO thin films grown on SrTiO 3 substrates and the impact of Ruddlesden–Popper (RP) faults. Using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and integrated differential phase contrast (iDPC) STEM imaging, we conducted atomic-scale structural and compositional analyses of OOV. Geometric phase analysis (GPA) was employed to measure the strain in fault-free and RP fault regions, while density functional theory (DFT) calculations explored different OOV arrangements in the LNO phase. Simulated iDPC-STEM imaging of energy-stabilized structures was performed to correlate with experimental results. Here, our findings reveal superstructure modulation in the chemical composition and atomic-scale lattice structure in LNO, primarily due to the formation of the OOV in Ni–O layers of the LaNiO 2.5 phase. The out-of-plane compressive strain of about 2% stabilizes this phase, reducing the strain, diminishing OOV, and transforming them into LNO.

36 MATERIALS SCIENCE↗

DOE OSTI2025

2D Vacancy Confinement in Anatase TiO 2 for Enhanced Photocatalytic Activities

Abstract Light‐driven energy conversion devices call for the atomic‐level manipulation of defects associated with electronic states in solids. However, previous approaches to produce oxygen vacancy (V O ) as a source of sub‐bandgap energy levels have hampered the precise control of the distribution and concentration ofV O . Here, a new strategy to spatially confineV O at the homo‐interfaces is demonstrated by exploiting the sequential growth of anatase TiO 2 under dissimilar thermodynamic conditions. Remarkably, metallic behavior with high carrier density and electron mobility is observed after sequential growth of the TiO 2 films under low pressure and temperature (L‐TiO 2 ) on top of high‐quality anatase TiO 2 epitaxial films (H‐TiO 2 ), despite the insulating properties of L‐TiO 2 and H‐TiO 2 single layers. Multiple characterizations elucidate that theV O layer is geometrically confined within 4 unit cells at the interface, along with low‐temperature crystallization of upper L‐TiO 2 films; this 2DV O layer is responsible for the formation of in‐gap states, promoting photocarrier lifetime (≈300%) and light absorption. These results suggest a synthetic strategy to locally confine functional defects and emphasize how sub‐bandgap energy levels in the confined imperfections influence the kinetics of light‐driven catalytic reactions.

Chemistry↗

DOE OSTI2023

The kinetics of the PuO 2 to Pu 2 O 3 conversion

Here in an oxidizing environment, the oxide formed on plutonium (Pu) metal is composed of a plutonium dioxide (PuO 2 ) top layer and a thin cubic plutonium sesquioxide (Pu 2 O 3 ) middle layer. In a reducing environment, the PuO 2 layer auto-reduces to cubic Pu 2 O 3 . The speed and extent of this conversion depend on the combination of temperature and time. While PuO 2 provides a strong diffusion barrier against unwanted Pu corrosion by gaseous species (like hydrogen), Pu 2 O 3 does not, since its crystal structure has chains of oxygen vacancies. The kinetics of the PuO 2 reduction are, therefore, of fundamental interest and enable researchers to better protect Pu from corrosion. In this report, the oxygen-diffusion-limited kinetics of the dioxide to sesquioxide conversion were obtained by dynamically heating a PuO 2 -covered Pu sample from 294 to 418 K in a high-vacuum vessel equipped with an in situ spectroscopic ellipsometer. The physical/chemical constraints in the conversion process were combined with the ellipsometry method of multi-sample analysis to track the percentage of PuO 2 and to compute the extent of Pu 2 O 3 formation. The resulting diffusion coefficients were compared against and then combined with complementary literature data to produce a comprehensive set of kinetic parameters for reliably modeling oxide conversion over a larger temperature range than spanned by prior studies. The extracted thermal activation energy barrier (43.7 kJ/mol) and pre-exponential factor (5.0 × 10 -10 cm 2 /s) for the oxygen-diffusion-limited process can be used to accurately model the PuO 2 to Pu 2 O 3 transformation in vacuum and/or inert gas applications.

36 MATERIALS SCIENCE↗

DOE OSTI2022

MOF-Transformed In 2 O 3-x @C Nanocorn Electrocatalyst for Efficient CO 2 Reduction to HCOOH

For electrochemical CO 2 reduction to HCOOH, an ongoing challenge is to design energy efficient electrocatalysts that can deliver a high HCOOH current density (J HCOOH ) at a low overpotential. Indium oxide is good HCOOH production catalyst but with low conductivity. In this work, we report a unique corn design of In 2 O 3-x @C nanocatalyst, wherein In 2 O 3-x nanocube as the fine grains dispersed uniformly on the carbon nanorod cob, resulting in the enhanced conductivity. Excellent performance is achieved with 84% Faradaic efficiency (FE) and 11 mA cm –2 J HCOOH at a low potential of – 0.4 V versus RHE. At the current density of 100 mA cm –2 , the applied potential remained stable for more than 120 h with the FE above 90%. Density functional theory calculations reveal that the abundant oxygen vacancy in In 2 O 3-x has exposed more In 3+ sites with activated electroactivity, which facilitates the formation of HCOO* intermediate. Operando X-ray absorption spectroscopy also confirms In 3+ as the active site and the key intermediate of HCOO* during the process of CO 2 reduction to HCOOH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗