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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Mechanistic and kinetic relevance of hydrogen and water in CO 2 hydrogenation on Cu-based catalysts

Here, we ally steady-state kinetics, kinetic isotope effects, and density functional theory (DFT) calculations to illustrate that Cu-based catalysts remain saturated by H-adatoms (H*) and molecular formic acid (HCOOH**) during CO 2 hydrogenation. High H* coverage under methanol synthesis conditions is evidenced by reverse water-gas shift (RWGS) rates that exhibit positive H 2 reaction orders only at P H2 ≲ 0.5 bar, above which methanol synthesis and RWGS rates exhibit first and zeroth order dependence on P H2 , respectively. HCOOH** also accumulates on the surface with increasing P CO2 as informed by the Langmuir-type dependence on P CO2 (0.25-23 bar) for both methanol synthesis and RWGS. As both HCOOH** and H* have one H-atom per site occupied, the two species share the same P H2 dependence and give rise to CO 2 reaction orders that are independent of P H2 . Surface coverages determined based on kinetic analyses are further corroborated with DFT-derived adsorption energies that show favorable HCOOH** adsorbate-adsorbate interactions as well as repulsive interactions for bidentate formate (HCOO**) on H*-saturated surfaces. Methanol selectivity remains invariant with P CO2 and P CO despite CO inhibiting reaction rates, thereby demonstrating methanol synthesis and RWGS occur on the same active site. In contrast, water preferentially inhibits methanol synthesis rates, increases methanol synthesis H 2 reaction order from 1.0 to 1.5, and alters the methanol synthesis H 2 /D 2 kinetic isotope effect; the inhibitory effect of H 2 O thus cannot be attributed to competitive adsorption alone and instead reflects a change in the rate-determining step for methanol synthesis. The disparate kinetics of methanol synthesis and RWGS evince a branching pathway where methanol is formed from formates and CO is formed from carboxylates. The presented work thus identifies the relevant surface species, underscores the distinct catalytic role of water in branching methanol synthesis and RWGS pathways, and, in doing so, details a mechanistic picture that yields predictable rates and reaction orders for both methanol synthesis and RWGS on Cu-based CO 2 hydrogenation catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Gas-mediated defect engineering in earth-abundant Mn-rich layered oxides for non-aqueous sodium-based batteries

Gases are often by-products of battery materials during cell formation and degradation, affecting the cycle life and safety of rechargeable batteries. However, understanding gas-mediated (electro)-chemical reactions and nanoscale structural transformations during the synthesis of battery electrode materials remains challenging because of the lack of suitable characterization routes and the complexity of the interplay between thermodynamics and kinetics. Here, in this study, we use operando synchrotron X-ray diffraction, in situ transmission X-ray microscopy and multiscale modelling to elucidate the reaction pathways and microstructural defect development of earth-abundant Mn-rich layered oxides as positive electrode materials for sodium-based batteries. In particular, we demonstrate the dominant role of CO 2 over O 2 and H 2 O (g) in modulating the competition between entropy and enthalpy during solid-state synthesis. Using Ni 0.25 Mn 0.75 CO 3 as a model precursor, we reveal that CO 2 generation favours the formation of entropy-driven metastable intermediates, suppresses closed pore/nanovoids formation and decreases chemical heterogeneity and residual lattice strain of Mn-rich layered oxides during the synthesis. This result motivates a fast-sintering strategy to promote CO 2 release, which ultimately leads to improved chemo-mechanical and electrochemical stability of the Mn-rich positive electrodes when tested in non-aqueous Na metal coin cells.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Pd-promoted reduction and restructuring of an In 2 O 3 -based catalyst for CO 2 hydrogenation at room temperature

An unconventional reaction mechanism in an In 2 O 3 /Pd(1 1 1) inverse model catalyst for the CO 2 hydrogenation reaction has been uncovered: In 2 O 3 is partially reduced at room temperature in a reaction atmosphere as a result of its direct contact with Pd(1 1 1), which is an efficient H 2 splitter. The reduction induces changes in surface free energy, leading to a dynamical restructuring at the In 2 O 3 /Pd(1 1 1) interface via formation of InO x and outward diffusion of Pd, as revealed by ambient pressure X-ray photoelectron spectroscopy, X-ray absorption spectroscopy and density functional theory simulations. This dynamical restructuring eventually promotes the growth of 2D InPd y O x nanodomains as the catalytically active phase and the exclusive formation of methanol upon hydrogenation of CO 2 at room temperature. A comparable high selectivity toward CH 3 OH was found in more realistic bulk catalytic systems (2 wt% Pd/In 2 O 3 catalyst and commercial CZA catalyst). Scanning tunneling microscopy under ultrahigh vacuum and ambient pressure reaction atmospheres further reveals the structural dynamics at the InO x /Pd(1 1 1) interface, where we follow in situ the evolution of the InO x particles on Pd(1 1 1) and the mobility of the InPd y O x nanodomains in a CO 2 + H 2 environment. The present findings of the formation of a mixed oxide phase in a dynamically restructuring metal/reducible-oxide interface indicate further implications for other heterogeneous catalytic systems beyond the present CO 2 hydrogenation example and highlight the importance of in situ investigations.

36 MATERIALS SCIENCE↗
DOE OSTI2024

The AUREX cell: a versatile operando electrochemical cell for studying catalytic materials using X-ray diffraction, total scattering and X-ray absorption spectroscopy under working conditions

Understanding the structure–property relationship in electrocatalysts under working conditions is crucial for the rational design of novel and improved catalytic materials. This paper presents the Aarhus University reactor for electrochemical studies using X-rays (AUREX) operando electrocatalytic flow cell, designed as an easy-to-use versatile setup with a minimal background contribution and a uniform flow field to limit concentration polarization and handle gas formation. The cell has been employed to measure operando total scattering, diffraction and absorption spectroscopy as well as simultaneous combinations thereof on a commercial silver electrocatalyst for proof of concept. This combination of operando techniques allows for monitoring of the short-, medium- and long-range structure under working conditions, including an applied potential, liquid electrolyte and local reaction environment. The structural transformations of the Ag electrocatalyst are monitored with non-negative matrix factorization, linear combination analysis, the Pearson correlation coefficient matrix, and refinements in both real and reciprocal space. Upon application of an oxidative potential in an Ar-saturated aqueous 0.1 M KHCO 3 /K 2 CO 3 electrolyte, the face-centered cubic (f.c.c.) Ag gradually transforms first to a trigonal Ag 2 CO 3 phase, followed by the formation of a monoclinic Ag 2 CO 3 phase. A reducing potential immediately reverts the structure to the Ag (f.c.c.) phase. Following the electrochemical-reaction-induced phase transitions is of fundamental interest and necessary for understanding and improving the stability of electrocatalysts, and the operando cell proves a versatile setup for probing this. In addition, it is demonstrated that, when studying electrochemical reactions, a high energy or short exposure time is needed to circumvent beam-induced effects.

Frank, Sara (ORCID:0000000163218363)↗
NASA NTRS1990

Observations of CO in the Magellanic irregular galaxy NGC 55

The content of molecular gas in galaxies, mainly H2, is one of the key observations necessary for the understanding of star formation processes and history. As the CO molecule is the most widely distributed molecule after H2 and has easily observable mm lines, it is used as a tracer for the molecular gas. CO was detected towards the direction where the H alpha and 6 cm radio continuum emission is strongest (Hummel et al. 1986). Here, researchers present the Gaussian line parameters in tabular form. The distribution of CO corresponds well with the intense HI cloud near the bar of NGC 55. The extent of the CO cloud is about 975 pc perpendicular to the major axis. As the radio continuum and the H alpha emission also peaks in this region, it is most probably associated with the star forming region in NGC 55. Assuming that the molecular gas is in virial equilibrium, researchers derive a mass of about 8 times 10(exp 7) solar magnitude. The molecular mass found indicates that the conversion factor for the molecular mass in Irr galaxies as inferred from CO line emission is indeed higher by up to a factor of 20 compared to the canonical value for the Galaxy.

Heithausen, Andreas↗
DOE OSTI2020

Activation and surface reactions of CO and H 2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions

Here, activation and surface reactions of CO and H 2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions were (quasi) in situ studied using temperature programmed surface reaction spectra, diffuse reflectance Fourier transform infrared spectroscopy, inelastic neutron scattering spectroscopy and electron paramagnetic resonance. CO undergoes disproportion reaction to produce gaseous CO 2 and surface carbon adatoms, and adsorbs to form surface formate species. H 2 adsorption forms dominant irreversibly-adsorbed surface hydroxyl groups and interstitial H species and very minor surface Zn-H species. Surface formate species and hydroxyl groups react to produce CO 2 and H 2 , while surface carbon adatoms are hydrogenated by surface Zn-H species sequentially to produce CH(a), CH 2 (a), CH 3 (a) and eventually gaseous CH 4 . The ZnO nanoplates, exposing a higher fraction of Zn-ZnO(0001) and O-ZnO(000–1) polar facets, are more active than the ZnO powders to catalyze CO hydrogenation to CH 4 . These results provide fundamental understanding of the reaction mechanisms and structural effects of CO hydrogenation reaction catalyzed by ZnO-based catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

Convective transport over the central United States and its role in regional CO and ozone budgets

We have constructed a regional budget for boundary layer carbon monoxide over the central United States (32.5 deg - 50 deg N, 90 deg - 105 deg W), emphasizing a detailed evaluation of deep convective vertical fluxes appropriate for the month of June. Deep convective venting of the boundary layer (upward) dominates other components of the CO budget, e.g., downward convective transport, loss of CO by oxidation, anthropogenic emissions, and CO produced from oxidation of methane, isoprene, and anthropogenic nonmethane hydrocarbons (NMHCs). Calculations of deep convective venting are based on the method pf Pickering et al.(1992a) which uses a satellite-derived deep convective cloud climatology along with transport statistics from convective cloud model simulations of observed prototype squall line events. This study uses analyses of convective episodes in 1985 and 1989 and CO measurements taken during several midwestern field campaigns. Deep convective venting of the boundary layer over this moderately polluted region provides a net (upward minus downward) flux of 18.1 x 10(exp 8) kg CO/month to the free troposphere during early summer. Shallow cumulus and synoptic-scale weather systems together make a comparable contribution (total net flux 16.2 x 10(exp 8) kg CO/month). Boundary layer venting of CO with other O3 precursors leads to efficient free troposheric O3 formation. We estimate that deep convective transport of CO and other precursors over the central United States in early summer leads to a gross production of 0.66 - 1.1 Gmol O3/d in good agreement with estimates of O3 production from boundary layer venting in a continental-scale model (Jacob et al., 1993a, b). On this respect the central U.S. region acts as s `chimney' for the country, and presumably this O3 contributes to high background levels of O3 in the eastern United States and O3 export to the North Atlantic.

Thompson, Anne M.↗
NASA NTRS1989

Hydrogen-silicon carbide interactions

A study of the thermochemistry and kinetics of hydrogen environmental attack of silicon carbide was conducted for temperatures in the range from 1100 C to 1400 C. Thermodynamic maps based on the parameters of pressure and oxygen/moisture content were constructed. With increasing moisture levels, four distinct regions of attack were identified. Each region is defined by the thermodynamically stable solid phases. The theoretically stable solid phases of Region 1 are silicon carbide and silicon. Experimental evidence is provided to support this thermodynamic prediction. Silicon carbide is the single stable solid phase in Region 2. Active attack of the silicon carbide in this region occurs by the formation of gases of SiO, CO, CH4, SiH4, and SiH. Analysis of the kinetics of reaction for Region 2 at 1300 C show the attack of the silicon carbide to be controlled by gas phase diffusion of H2O to the sample. Silicon carbide and silica are the stable phases common to Regions 3 and 4. These two regions are characterized by the passive oxidation of silicon carbide and formation of a protective silica layer.

Eckel, Andrew J.↗
NASA NTRS1990

Hydrogen-silicon carbide interactions

A study of the thermochemistry and kinetics of hydrogen environmental attack of silicon carbide was conducted for temperatures in the range from 1100 C to 1400 C. Thermodynamics maps based on the parameters of pressure and oxygen/moisture content were constructed. With increasing moisture levels, four distinct regions of attack were identified. Each region is defined by the thermodynamically stable solid phases. The theoretically stable solid phases of region 1 are silicon carbide and silicon. Experimental evidence is provided to support this thermodynamic prediction. Silicone carbide is the single stable solid phase in region 2. Active attack of the silicon carbide in this region occurs by the formation of gases of SiO, CO, CH4, SiH4 and SiH. Analyses of the kinetics of reaction for region 2 at 1300 C show the attack of the silicon carbide to be controlled by gas phase diffusion of H2O to the sample. Silicon carbide and silica are the stable phases common to regions 3 and 4. These two regions are characterized by the passive oxidation of silicon carbide and formation of a protective silica layer.

Eckel, Andrew J.↗
NASA NTRS1991

Inelastic and reactive scattering of hyperthermal atomic oxygen from amorphous carbon

The reaction of hyperthermal oxygen atoms with an amorphous carbon-13 surface was studied using a modified universal crossed molecular beams apparatus. Time-of-flight distributions of inelastically scattered O-atoms and reactively scattered CO-13 and CO2-13 were measured with a rotatable mass spectrometer detector. Two inelastic scattering channels were observed, corresponding to a direct inelastic process in which the scattered O-atoms retain 20 to 30 percent of their initial kinetic energy and to a trapping desorption process whereby O-atoms emerge from the surface at thermal velocities. Reactive scattering data imply the formation of two kinds of CO products, slow products whose translational energies are determined by the surface temperature and hyperthermal (Approx. 3 eV) products with translational energies comprising roughly 30 percent of the total available energy (E sub avl), where E sub avl is the sum of the collision energy and the reaction exothermicity. Angular data show that the hyperthermal CO is scattered preferentially in the specular direction. CO2 product was also observed, but at much lower intensities than CO and with only thermal velocities.

Minton, Timothy K.↗
NASA NTRS1990

Molecular gas and star formation in the centers of Virgo spirals

The CO and H alpha flux distributions for a sample of Virgo spirals were mapped out in an attempt to understand the coupling between gas dynamics and star formation in spiral galaxies. A broad range of morphological types were observed (types Sab through Scd) under the hypothesis that the gas dynamics is most influential in determining the overall appearance of a spiral galaxy. Only non-barred spirals were considered so that the well-studied but complicated properties of bars and their role in inducing star formation would not be a factor. All galaxies were chosen from the Virgo cluster to eliminate uncertainties due to distance errors. Since the dynamical seat of a spiral is at its center, it was expected that the dynamics of the central region would influence global properties of the rest of the disk. This could happen through the existence or absence of an inner Lindblad resonance (according to the degree of central concentration of mass) to modulate swing amplification of spiral waves, or the persistence of an oval distortion to initiate an instability which leads to spiral structure.

Canzian, Blaise↗
DOE OSTI2021

Ab Initio Modeling of fcc Fe-Co-Cr-Ni High Entropy Alloys with Full Composition Range

The Fe-Co-Cr-Ni quaternary system has been studied extensively in the past decade, not only because of the superior properties achieved like high tensile ductility and fracture toughness, but also it is the foundation for the development of FeCrCoNi-based HEAs. However, most of the investigations are mainly focusing on the equiatomic and semi-equiatomic compositions. The physical properties of non-equiatomic compositions are barely explored. In the current work, the ab initio approach is adopted to predict the lattice parameter, structure stabilities, elastic properties, and enthalpy of formations of fcc Fe-Cr-Co-Ni HEA single crystals with the special quasirandom structure (SQS) method. To expand the design of Fe-Co-Cr-Ni HEAs into a full composition range, the current simulations cover all the binaries, ternaries, and the whole quaternary system. The 2-D composition-property contour diagrams are created to show the physical properties in the ternary and quaternary systems. Furthermore, our investigation shows that the fcc alloys' lattice parameter increases with the addition of Fe and Cr and decreases with Ni and Co. In addition to the enthalpy of formation at o K, the shape distortion rate is proposed to be another essential parameter to evaluate crystal stability. The results show the addition of Cr would destabilize the fcc lattice and cause symmetry breaking. Finally, the result of Pugh’s ratio shows that most of the fcc alloys show ductile behavior (P > 1.75), especially for the alloys around Fe 3 Ni, FeCo, and Fe 2 NiCo (P > 2.5). The brittle behavior (P < 1.75) is located around Fe 3 Cr and Fe 2 CoCr. Meanwhile, Cr 2 NiCo and Cr 2 FeNiCo are considered promising compositions to be tried and verified experimentally because of the higher bulk modulus and moderate shear modulus.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Operando NRIXS and XAFS Investigation of Segregation Phenomena in Fe-Cu and Fe-Ag Nanoparticle Catalysts during CO 2 Electroreduction

Operando nuclear resonant inelastic X-ray scattering (NRIXS) and X-ray absorption fine-structure spectroscopy (XAFS) measurements were used to gain insight into the structure and surface composition of FeCu and FeAg nanoparticles (NPs) during the electrochemical CO 2 reduction (CO 2 RR) and to extract correlations with their catalytic activity and selectivity. The formation of a core–shell structure during CO 2 RR for FeAg NPs was inferred from the analysis of the operando NRIXS data (phonon density of states, PDOS) and XAFS measurements. Electrochemical analysis of the FeAg NPs revealed a faradaic selectivity of 36 % for CO in 0.1 M KHCO 3 at -1.1 V vs. RHE, similar to that of pure Ag NPs. In contrast, a predominant selectivity towards H 2 evolution is obtained in the case of the FeCu NPs, analogous to the results obtained for pure Fe NPs, although small Cu NPs have also been shown to favor H 2 production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Intermolecular Proton Transfer Enabled Reactive CO 2 Capture by the Malononitrile Anion

Task-specific ionic liquids (ILs) employing carbanions represent a new class of ILs for carbon capture. The deprotonated malononitrile carbanion, [CH(CN) 2 ] - , has shown close to equimolar capacity for reactive CO 2 capture. Although the formation of the [C(CN) 2 COOH] - carboxylic acid was found to be the final product, how the hydrogen atom on the [CH(CN) 2 ] - carbanion transfers to the carboxylate group as a proton has not been fully understood. In this work, we employ density functional theory calculations with an implicit solvation model to investigate the proton transfer mechanisms in forming carboxylic acid from the reaction of the [CH(CN) 2 ] - carbanion with CO 2 . We find that the intramolecular proton-transfer pathway in [CH(CN) 2 COO] - to form [C(CN) 2 COOH] - is unlikely due to the high energy barrier of 152 kJ/mol. Instead, the intermolecular proton transfer pathway between two [CH(CN) 2 COO] - anions is more feasible to form two molecules of [C(CN) 2 COOH] - , with a significantly lower activation energy of 50 kJ/mol. Moreover, the [C(CN) 2 COOH] - dimer is further stabilized by the intermolecular hydrogen bonds of the two –COOH groups in the Z-configuration of the π-conjugated planar geometry. This insight of reactive CO 2 capture enabled by intermolecular proton transfer will be useful in designing novel carbanions and ILs for carbon capture and conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Transient kinetic insights into selective propene oxidation over industrial bismuth molybdate catalysts

Selective oxidation of propene to acrolein over industrial multicomponent bismuth molybdate (BMO) catalysts significantly depends on reaction conditions that include operating parameters and catalyst state. Here, this work investigates selective propene oxidation in the intrinsic kinetic paradigm of Temporal Analysis of Products (TAP) reactor by systematically varying catalyst redox state, temperature, and oxygen-to-propene feed ratio. A 93 % propene conversion with an acrolein yield of 80 % is achieved at elevated temperatures (450 °C) on oxidized catalysts under oxygen-rich conditions (O 2 :C 3 H 6 = 10). However, these conditions diminish acrolein-to-CO 2 selectivity due to enhanced total oxidation to CO 2 . In contrast, a reduced catalyst state, moderate temperature (350 °C), and lower oxygen feed (O 2 :C 3 H 6 = 1) nearly doubles the acrolein to-CO 2 selectivity, albeit at a lower acrolein yield (33 %). Transient kinetic studies together with a kinetic model that simplify the major product formation pathways in lumped non-elementary forms reveal that the availability of surface oxygen species plays a pivotal role in governing reaction pathways. Additionally, density functional theory (DFT) calculations on pure BMO catalysts inform the role of surface redox states on propene and oxygen activation barriers. Lattice oxygen at acrolein-selective sites drives both acrolein and CO 2 formation, while adsorbed oxygen at activation sites favors unselective CO 2 generation. This work establishes a critical relationship between transient product selectivity and surface oxygen availability, which is strongly influenced by catalyst redox state, feed ratio, and reaction temperature. These insights underscore the importance of dynamic reactor operation strategies and offer a foundation for designing next-generation propene oxidation processes with tunable acrolein selectivity.

42 - ENGINEERING↗
DOE OSTI2023

Adsorbate-Induced Adatom Formation on Lithium, Iron, Cobalt, Ruthenium, and Rhenium Surfaces

Recent experimental and theoretical studies have demonstrated the reaction-driven metal–metal bond breaking in metal catalytic surfaces even under relatively mild conditions. Here, we construct a density functional theory (DFT) database for the adsorbate-induced adatom formation energy on the close-packed facets of three hexagonal close-packed metals (Co, Ru, and Re) and two body-centered cubic metals (Li and Fe), where the source of the ejected metal atom is either a step edge or a close-packed surface. For Co and Ru, we also considered their metastable face-centered cubic structures. We studied 18 different adsorbates relevant to catalytic processes and predicted noticeably easier adatom formation on Li and Fe compared to the other three metals. The NH 3 - and CO-induced adatom formation on Fe(110) is possible at room temperature, a result relevant to NH 3 synthesis and Fischer-Tropsch synthesis, respectively. There also exist other systems with favorable adsorbate effects for adatom formation relevant to catalytic processes at elevated temperatures (500–700 K). Our results offer insight into the reaction-driven formation of metal clusters, which could play the role of active sites in reactions catalyzed by Li, Fe, Co, Ru, and Re catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2003

Iron catalyst chemistry in modeling a high-pressure carbon monoxide nanotube reactor

The high-pressure carbon monoxide (HiPco) technique for producing single-wall carbon nanotubes (SWNTs) is analyzed with the use of a chemical reaction model coupled with flow properties calculated along streamlines, calculated by the FLUENT code for pure carbon monoxide. Cold iron pentacarbonyl, diluted in CO at about 30 atmospheres, is injected into a conical mixing zone, where hot CO is also introduced via three jets at 30 degrees with respect to the axis. Hot CO decomposes the Fe(CO)5 to release atomic Fe. Then iron nucleates and forms clusters that catalyze the formation of SWNTs by a disproportionation reaction (Boudouard) of CO on Fe-containing clusters. Alternative nucleation rates are estimated from the theory of hard sphere collision dynamics with an activation energy barrier. The rate coefficient for carbon nanotube growth is estimated from activation energies in the literature. The calculated growth was found be about an order of magnitude greater than measured, regardless of the nucleation rate. A study of cluster formation in an incubation zone prior to injection into the reactor shows that direct dimer formation from Fe atoms is not as important as formation via an exchange reaction of Fe with CO in FeCO.

Evaluation Studies↗
DOE OSTI2020

Catalytic C 2 H 2 synthesis via low temperature CO hydrogenation on defect-rich 2D-MoS 2 and 2D-MoS 2 decorated with Mo clusters

Rational design of novel catalytic materials used to synthesize storable fuels via the CO hydrogenation reaction has recently received considerable attention. In this work, defect poor and defect rich 2D-MoS 2 as well as 2D-MoS 2 decorated with Mo clusters are employed as catalysts for the generation of acetylene (C 2 H 2 ) via the CO hydrogenation reaction. Temperature programmed desorption is used to study the interaction of CO and H2 molecules with the MoS 2 surface as well as the formation of reaction products. The experiments indicate the presence of four CO adsorption sites below room temperature and a competitive adsorption between the CO and H 2 molecules. The investigations show that CO hydrogenation is not possible on defect poor MoS 2 at low temperatures. However, on defect rich 2D-MoS 2 , small amounts of C 2 H 2 are produced, which desorb from the surface at temperatures between 170 K and 250 K. A similar C 2 H 2 signal is detected from defect poor 2D-MoS 2 decorated with Mo clusters, which indicates that low coordinated Mo atoms on 2D-MoS 2 are responsible for the formation of C 2 H 2 . Density functional theory investigations are performed to explore possible adsorption sites of CO and understand the formation mechanism of C 2 H 2 on MoS 2 and Mo 7 /MoS 2 . The theoretical investigation indicates a strong binding of C 2 H 2 on the Mo sites of MoS 2 preventing the direct desorption of C 2 H 2 at low temperatures as observed experimentally. Instead, the theoretical results suggest that the experimental data are consistent with a mechanism in which CHO radical dimers lead to the formation of C 2 H 2 that presents an exothermic desorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗