Theoretical Study of Electrocatalytic CO2 Reduction Mechanism on Typical MXenes under Realistic Conditions.

MXenes are a revolutionary class of two-dimensional materials that have been recently demonstrated to exhibit promising capability of electrocatalytic CO2 reduction reaction (CO2RR) in theory and experiment. In electrocatalytic reactions, the active phases, the mechanism, and the performance can be greatly influenced by electrochemical conditions such as applied electrode potential, pH, and electrolyte. Therefore, in this first-principles study, the stable surface structures of three typical MXenes (V2C, Mo2C, and Ti3C2) with variation of electrocatalytic conditions were determined by the Pourbaix phase diagrams. Additionally, the reaction mechanism for CO2RR toward C1 products was investigated based on the thermal dynamically stable phases. The computation revealed that surfaces of all three MXenes are dominated by H* termination throughout the practical CO2RR electrochemical condition ranges. Meanwhile, the bicarbonate ions, which serve as the major electrolyte in CO2RR, show thermal dynamic unfavorability to adsorb on the surfaces. Among the three types of MXenes, V2CH exhibits higher activity in generating CO and HCOOH through the CO2RR, while Mo2CH exhibits higher activity in producing HCHO, CH3OH, and CH4. This comprehensive study provides crucial insights into the mechanism of electrocatalytic CO2RR on MXenes under realistic electrochemical conditions.

Photodissociation study of CO2 on the formation of state-correlated CO(X1Σ+, v) with O(3P2) photoproducts in the low energy band centered at 148 nm.

The spin-forbidden O(3P2) + CO(X1Σ+, v) channel formed from the photodissociation of CO2 in the low energy band centered at 148 nm is investigated by using the time-sliced velocity-mapped ion imaging technique. The vibrational-resolved images of the O(3P2) photoproducts measured in the photolysis wavelength range of 144.62-150.45 nm are analyzed to give the total kinetic energy releases (TKER) spectra, CO(X1Σ+) vibrational state distributions, and anisotropy parameters (ß). The TKER spectra reveal the formation of correlated CO(X1Σ+) with well resolved v = 0-10 (or 11) vibrational bands. Several high vibrational bands that were observed in the low TKER region for each studied photolysis wavelength exhibit a bimodal structure. The CO(X1Σ+, v) vibrational distributions all present inverted characteristics, and the most populated vibrational state changes from a low vibrational state to a relatively higher vibrational state with a change in the photolysis wavelength from 150.45 to 144.62 nm. However, the vibrational-state specific ß-values for different photolysis wavelengths present a similar variation trend. The measured ß-values show a significant bulge at the higher vibrational levels, in addition to the overall slow decreasing trend. The observed bimodal structures with mutational ß-values for the high vibrational excited state CO(1Σ+) photoproducts suggest the existence of more than one nonadiabatic pathway with different anisotropies in the formation of O(3P2) + CO(X1Σ+, v) photoproducts across the low energy band.

Effects of C-H stretching excitation on the dynamics of the O(1D) + CHD3 → OH/OD + CD3/CHD2 reaction.

The vibrationally excited reaction O(1D) + CHD3(ν1 = 1) has been investigated by crossed-molecular-beam experiments with a time-sliced velocity map imaging technique. Detailed and quantitative information is extracted on the C-H stretching excitation effects on the reactivity and dynamics of the title reaction, with the help of preparation of C-H stretching excited CHD3 molecules by direct infrared excitation. Experimental results show that the vibrational stretching excitation of the C-H bond almost does not affect the relative contributions between different dynamical pathways for all product channels. For the OH + CD3 product channel, the vibrational energy of the C-H stretching excited CHD3 reagent is channeled exclusively into the vibrational energy of the OH products. The vibrational excitation of the CHD3 reactant changes the reactivities for the ground-state and umbrella-mode-excited CD3 channels very modestly, while it significantly suppresses the corresponding CHD2 channels. For the CHD2(ν1 = 1) channel, the stretching excited C-H bond of the CHD3 molecule acts almost as a pure spectator.

Formation of 1-ethynyl-1H-silole from the reaction of silicon atoms with benzene: matrix infrared spectroscopy and quantum chemical calculations.

The reaction of silicon atoms with benzene molecules in solid neon is studied using matrix isolation infrared spectroscopy. Aided by carbon-13 and deuterium isotopic shifts as well as quantum-chemical calculations, the reaction intermediates and products are safely assigned. Among them, silicon atom addition to the aromatic π-system of benzene occurs in a [1,4] fashion Si[η2(1,4)-C6H6] complex (A) has been formed spontaneously on annealing, which further isomerizes to the seven-membered ring 1-silacycloheptatrienylidene (B) under UV light irradiation. A previously unconsidered five-membered ring 1-ethynyl-1H-silole (C) is generated as the final product under broadband UV light irradiation. The underlying reaction mechanism of complex A photo-isomerizing to species B and C is discussed in detail, which shows a remarkable boron-silicon diagonal relationship as compared to the reaction of boron with benzene in forming borole derivatives. The results presented herein provide new insight into the future design and synthesis of corresponding silole derivatives.

Vacuum ultraviolet photodissociation of OCS via the 21Σ+ state: the S(1D2) elimination channel.

The photodissociation of OCS is necessary to model the primary photochemical processes of OCS in the global cycling of sulfur and interstellar photochemistry. Here, by combining the time-sliced velocity-map ion imaging technique with the single vacuum ultraviolet photon ionization method, we have studied the CO(1Σ+, v) + S(1D2) photoproduct channel from the OCS photodissociation via the eight different vibrational resonances ( = 1-8) in the 21Σ+(, 1, 0) ← X1Σ+(0, 0, 0) band. From the measured S(1D2) images, the wavelength-dependent CO(1Σ+, v) vibrational state populations have been obtained in the wavelength range of 142.98-154.37 nm. The majority of the CO(1Σ+, v) photoproducts are shown to abruptly populate from low vibrational states to high vibrational states as the photolysis wavelength decreases from 152.38 to 148.92 nm. The anisotropy parameters (ß) for the CO(1Σ+, v) + S(1D2) channel have also been determined from the images of the S(1D2) photoproducts. It is found that the vibrational state-specific ß-values present a similar decreasing trend with increasing CO vibrational excitation for all the eight vibrational resonances of OCS*(21Σ+). These observations indicate that there is a possibility that more than one non-adiabatic dissociation pathways with different dissociation lifetimes are involved in the formation of CO(1Σ+) + S(1D2) photoproducts from the initial vibronic levels of the 21Σ+ state to the final dissociative state.

Observation of unsaturated platinum carbenes Pt2C2n - (n = 1-3) clusters: A photoelectron imaging spectroscopic and theoretical study.

The structural and bonding properties of the Pt2C2n - (n = 1-3) complexes have been investigated by mass-selected photoelectron velocity-map imaging spectroscopy with quantum chemical calculations. The adiabatic detachment energies and vertical detachment energies of Pt2C2n - have been obtained from the measured photoelectron imaging spectra. Theoretical results indicate that the lowest-energy isomers of Pt2C2n - (n = 1-3) possess linear chain-shaped configurations. The binding motif in the most stable isomer of Pt2C2 - has a linear cumulenic structure with a Pt=C=C=Pt configuration, and the structural characteristic persists up to all the lowest-energy isomers of the Pt2C4 - and Pt2C6 - anions. The chemical bonding analyses indicate that the Pt2C2n - (n = 1-3) complexes have multicenter two-electron characteristics.

Unraveling Charge State of Supported Au Single-Atoms during CO Oxidation.

Thermally stable Au single-atoms supported by monolayered CuO grown at Cu(110) have been successfully prepared. The charge transfer from the CuO support to single Au atoms is confirmed to play a key role in tuning the activity for CO oxidation. Initially, the negatively charged Au single-atom is active for CO oxidation with its adjacent lattice O atom depleted to generate an O vacancy in the CuO monolayer. Afterward, the Au single-atom is neutralized, preventing further CO reaction. The produced O vacancy can be healed by exposure to O2 at 400 K and accordingly the reaction activity is restored.

Photoinduced decomposition of acetaldehyde on a reduced TiO2(110) surface: involvement of lattice oxygen.

We have investigated the photo-induced decomposition of acetaldehyde (CH3CHO) on TiO2(110) at 400 nm using temperature programmed desorption (TPD) and time of flight (TOF) methods. Formate (HCOO-) and acetate (CH3COO-) products have been detected. The initial step in the decomposition of CH3CHO on TiO2(110) is the formation of a CH3CHO bidentate intermediate in which the carbonyl O atom of CH3CHO is bound to the five-fold-coordinated Ti4+ lattice site (Ti5c) and the carbonyl C atom is bound to a nearby bridge-bonded oxygen (BBO) atom. During 400 nm irradiation, the decomposition of the CH3CHO bidentate mainly occurs through two parallel pathways. Part of the CH3CHO bidentate on the surface undergoes a facile photoreaction to form formate by ejecting the methyl radical of CH3CHO into gas phase. The remaining CH3CHO bidentate reacts on the surface to produce acetate by transferring the H atom of -CHO to a BBO site or by ejecting the H atom into the vacuum. Thus we have found that BBO atoms are intimately involved in the photo-induced decomposition of CH3CHO on TiO2(110).

Molecular hydrogen formation from photocatalysis of methanol on anatase-TiO2(101).

Photocatalysis of methanol (CH3OH) on anatase (A)-TiO2(101) has been investigated using temperature programmed desorption (TPD) method with 266 nm light at low surface temperatures. Experimental results show that CH3OH adsorbs on the A-TiO2(101) surface predominantly in molecular form, with only a small amount of CH3OH in dissociated form. Photocatalytic products, formaldehyde (CH2O) and methyl formate (HCOOCH3), have been detected under 266 nm light irradiation. In addition to H2O formation, H2 product is also observed by TPD spectroscopy. Experimental results indicate that H2 product is formed via thermal recombination of H-atoms on the BBO sites from photocatalysis of CH3OH on the A-TiO2(101) surface, and H2 production on the A-TiO2(101) surface is significantly more efficient than that on the rutile (R)-TiO2(110) surface.

Molecular hydrogen formation from photocatalysis of methanol on TiO2(110).

It is well established that adding methanol to water could significantly enhance H2 production by TiO2. Recently, we have found that methanol can be photocatalytically dissociated on TiO2(110) at 400 nm via a stepwise mechanism. However, how molecular hydrogen can be formed from the photocatalyzed methanol/TiO2(110) surface is still not clear. In this work, we have investigated deuterium formation from photocatalysis of the fully deuterated methanol (CD3OD) on TiO2(110) at 400 nm using a temperature programmed desorption (TPD) technique. Photocatalytic dissociation products formaldehyde (CD2O) and D-atoms on BBO sites (via D2O TPD product) have been detected. In addition to D2O formation by heating the photocatalyzed methanol/TiO2(110) surface, we have also observed D2 product formation. D2 is clearly formed via thermal recombination of the D-atoms on the BBO sites from photocatalysis of methanol. Experimental results indicate that D2O formation is more important than D2 formation and that D2 formation is clearly affected by the D2O formation process.

Strong photon energy dependence of the photocatalytic dissociation rate of methanol on TiO2(110).

Photocatalytic dissociation of methanol (CH3OH) on a TiO2(110) surface has been studied by temperature programmed desorption (TPD) at 355 and 266 nm. Primary dissociation products, CH2O and H atoms, have been detected. The dependence of the reactant and product TPD signals on irradiation time has been measured, allowing the photocatalytic reaction rate of CH3OH at both wavelengths to be directly determined. The initial dissociation rate of CH3OH at 266 nm is nearly 2 orders of magnitude faster than that at 355 nm, suggesting that CH3OH photocatalysis is strongly dependent on photon energy. This experimental result raises doubt about the widely accepted photocatalysis model on TiO2, which assumes that the excess potential energy of charge carriers is lost to the lattice via strong coupling with phonon modes by very fast thermalization and the reaction of the adsorbate is thus only dependent on the number of electron-hole pairs created by photoexcitation.

Direct Visualization of CO Interaction on Oxygen Poisoned Co(0001).

The poisoning of catalysts has always been a vital issue in catalytic reactions. In this study, direct observation of the interaction of CO and oxygen-poisoned Co(0001) has been achieved with scanning tunneling microscopy (STM), temperature-programmed desorption (TPD), and density functional theory calculation. A two-stage adsorption process of CO on a well-prepared p(2×2)-O layer covered Co(0001) was directly visualized. With increasing annealing time at a certain temperature after the CO dosage, the ordered (2 × 2) pattern formed in the first stage can be recovered, suggesting the weak interaction of CO with the O-covered Co(0001) surface in the latter stage. Compared to the clean Co(0001) surface, on an oxygen-poisoned surface, no further reaction was observed, illustrating the poisoning of the catalyst. Moreover, TPD results are in good agreement with the STM observation; a desorption energy of 0.35 eV is evaluated with a simple but accurate scheme.

Stepwise photocatalytic dissociation of methanol and water on TiO2(110).

We have investigated the photocatalysis of partially deuterated methanol (CD(3)OH) and H(2)O on TiO(2)(110) at 400 nm using a newly developed photocatalysis apparatus in combination with theoretical calculations. Photocatalyzed products, CD(2)O on Ti(5c) sites, and H and D atoms on bridge-bonded oxygen (BBO) sites from CD(3)OH have been clearly detected, while no evidence of H(2)O photocatalysis was found. The experimental results show that dissociation of CD(3)OH on TiO(2)(110) occurs in a stepwise manner in which the O-H dissociation proceeds first and is then followed by C-D dissociation. Theoretical calculations indicate that the high reverse barrier to C-D recombination and the facile desorption of CD(2)O make photocatalytic methanol dissociation on TiO(2)(110) proceed efficiently. Theoretical results also reveal that the reverse reactions, i.e, O-H recombination after H(2)O photocatalytic dissociation on TiO(2)(110), may occur easily, thus inhibiting efficient photocatalytic water splitting.

Isoelectronic IrC3-, PtC3, and AuC3+ Clusters Featuring the Structural and Bonding Resemblance to OC3.

The IrC3- and PtC3- anions generated by laser vaporization were identified and characterized by gas-phase photoelectron spectroscopy and quantum-chemical calculations. The straight-chain structures with an MCCC (M = metal; C = carbon) connectivity are found for the isoelectronic IrC3-, PtC3, and AuC3+ clusters. Further elaborate analyses manifest the strikingly structural and bonding similarities between MC3-/0/+ clusters and OC3 revealed. This finding has broadened the notion of autogenic isolobality to the gas-phase clusters that contain Ir-, Pt, Au+, and C centers.

Atomic-Scale Observation of Sequential Oxidation Process on Co(0001).

Oxygen dissociation and activation on surfaces play a crucial role in heterogeneous catalysis and oxidation processes. In this study, we have conducted a series of scanning tunneling microscopy (STM) experiments combined with density functional theory calculation to investigate the oxidation process in a single crystal Co(0001) surface. For the first time, we show a comprehensive in situ STM study of the oxidation process of Co(0001) from an atomic point of view. With low O2 exposure at 90 K, chemisorbed oxygen pairs are observed showing a dumbbell-like STM feature. At a relatively higher temperature range of 160-250 K, a large-scale p(2 × 2)-O adlayer forms and the O adatoms show surprisingly high mobility. With the temperature of Co(0001) kept at ≥300 K, adsorption of oxygen leads to fast oxidation of the surface to amorphous cotton-like protrusions, which occur initially at the step/edge sites and interstitial defect sites.

Effect of the Hydrogen Bond in Photoinduced Water Dissociation: A Double-Edged Sword.

Photoinduced water dissociation on rutile-TiO2 was investigated using various methods. Experimental results reveal that the water dissociation occurs via transferring an H atom to a bridge bonded oxygen site and ejecting an OH radical to the gas phase during irradiation. The reaction is strongly suppressed as the water coverage increases. Further scanning tunneling microscopy study demonstrates that hydrogen bonds between water molecules have a dramatic effect on the reaction. Interestingly, a single hydrogen bond in water dimer enhances the water dissociation reaction, while one-dimensional hydrogen bonds in water chains inhibit the reaction. Density functional theory calculations indicate that the effect of hydrogen bonds on the OH dissociation energy is likely the origin of this remarkable behavior. The results suggest that avoiding a strong hydrogen bond network between water molecules is crucial for water splitting.