Visualizing the Promoting Role of Interfacial Water in the Deprotonation of Formic Acid on Cu(111).

Water plays a crucial role in various heterogeneous catalytic reactions, but the atomic-scale characterization of how water participates in these chemical processes remains a significant challenge. Here we directly visualize the promoting role of interfacial water in the deprotonation of formic acid (FA) on a metal surface, using combined scanning tunneling microscopy and qPlus-based noncontact atomic force microscopy. We find the dissociation of FA when coadsorbed with water on the Cu(111) surface, resulting in the formation of hydronium and formate ions. Interestingly, most of the hydrated proton and formate ions exhibit a phase-separated behavior on Cu(111), in which Eigen and Zundel cations assemble into a monolayer hexagonal hydrogen-bonding (H-bonding) network, and bidentate formate ions are solvated with water and aggregate into one-dimensional chains or two-dimensional H-bonding networks. This phase-separated behavior is essential for preventing the proton transfer back from hydronium to formate and the reformation of FA. Density functional theory calculations reveal that the participation of water significantly reduces the deprotonation barrier of FA on Cu(111), in which water catalyzes the decomposition of FA through the Grotthuss proton transfer mechanism. In addition, the separate solvation of hydronium and bidentate formate ions is energetically preferred due to the enhanced interaction with the copper substrate. The promoting role of water in the deprotonation of FA is further confirmed by the temperature-programmed desorption experiment, which shows that the intensity of the H2 desorption peak significantly increases and the desorption of FA declines when water and FA coadsorbed on the Cu(111) surface.

Wavelength-Dependent Activity of Oxygen Species in Propane Conversion on Rutile TiO2(110).

Photocatalytic oxidative dehydrogenation of propane (C3H8) into propene (C3H6) under mild conditions holds great potential in the chemical industry, but understanding how active species participate in C3H8 conversion remains a significant challenge. Here, the wavelength-dependent activities of bridging oxygen (Ob2-) and the Ti5c-bound oxygen adatom (OTi2-) of model rutile (R) TiO2(110) in C3H8 conversion have been investigated. Under 257 and 343 nm irradiation, hole-trapped OTi- and Ob- can abstract the hydrogen atom of C3H8, forming the CH3CH•CH3 radical and C3H6. However, the rate of C3H8 conversion with hole-trapped Ob- is strongly dependent on the wavelength, primarily producing the C3H7• radical. In the case of hole-trapped OTi-, C3H6 is the main product, which is nearly independent of wavelength. The differences in the wavelength-dependent activity and product selectivity are likely due to dynamic control rather than thermodynamic control. The result provides a deeper understanding of the dynamic processes involved in the conversion of light alkanes in TiO2 photocatalysis.

Low-Temperature Oxidation of Methane on Rutile TiO2(110): Identifying the Role of Surface Oxygen Species.

Understanding the microkinetic mechanism underlying photocatalytic oxidative methane (CH4) conversion is of significant importance for the successful design of efficient catalysts. Herein, CH4 photooxidation has been systematically investigated on oxidized rutile(R)-TiO2(110) at 60 K. Under 355 nm irradiation, the C-H bond activation of CH4 is accomplished by the hole-trapped dangling OTi- center rather than the hole-trapped Ob- center via the Eley-Rideal reaction pathway, producing movable CH3• radicals. Subsequently, movable CH3• radicals encounter an O/OH species to form CH3O/CH3OH species, which could further dissociate into CH2O under irradiation. However, the majority of the CH3• radical intermediate is ejected into a vacuum, which may induce radical-mediated reactions under ambient conditions. The result not only advances our knowledge about inert C-H bond activation but also provides a deep insight into the mechanism of photocatalytic CH4 conversion, which will be helpful for the successful design of efficient catalysts.

Low-Temperature Ethylbenzene Conversion on Rutile TiO2(100) via Photocatalysis: The Strong Photon Energy Dependence.

Direct dehydrogenation of alkanes under mild conditions offers a green route to produce valuable olefins, but realizing C-H bond activation at a low temperature presents a significant challenge. Here, photocatalytic ethylbenzene conversion into styrene has been achieved by one hole on rutile (R)-TiO2(100) at 80 K under 257 and 343 nm irradiation. Although the rates of the initial α-C-H bond activation are nearly the same at the two wavelengths, the rate of the ß-C-H bond cleavage is strongly dependent upon hole energy, leading to the much higher yield of 290 K styrene formation at 257 nm, which raises doubt about the simplified TiO2 photocatalysis model in which excess energy of the charge carrier is useless and highlights the importance of intermolecular energy redistribution in photocatalytic reactions. The result not only advances our understandings in low-temperature C-H bond activation but also calls for the development of a more sophisticated photocatalysis model.

Photocatalytic ethane conversion on rutile TiO2(110): identifying the role of the ethyl radical.

Oxidative dehydrogenation of ethane (C2H6, ODHE) is a promising approach to producing ethene (C2H4) in the chemical industry. However, the ODHE needs to be operated at a high temperature, and realizing the ODHE under mild conditions is still a big challenge. Herein, using photocatalytic ODHE to obtain C2H4 has been achieved successfully on a model rutile(R)-TiO2(110) surface with high selectivity. Initially, the C2H6 reacts with hole trapped OTi- centers to produce ethyl radicals , which can be precisely detected by a sensitive TOF method, and then the majority of the radicals spontaneously dehydrogenate into C2H4 without another photo-generated hole. In addition, parts of the radicals rebound with diversified surface sites to produce C2 products via migration along the surface. The mechanistic model built in this work not only advances our knowledge of the C-H bond activation and low temperature C2H6 conversion, but also provides new opportunities for realizing the ODHE with high C2H4 efficiency under mild conditions.

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.

Photocatalytic Oxidative Dehydrogenation of Propane for Selective Propene Production with TiO2.

Oxidative dehydrogenation of propane (ODHP) as an exothermic process is a promising method to produce propene (C3H6) with lower energy consumption in chemical industry. However, the selectivity of the C3H6 product is always poor because of overoxidation. Herein, the ODHP reaction into C3H6 on a model rutile(R)-TiO2(110) surface at low temperature via photocatalysis has been realized successfully. The results illustrate that photocatalytic oxidative dehydrogenation of propane (C3H8) into C3H6 can occur efficiently on R-TiO2(110) at 90 K via a stepwise manner, in which the initial C-H cleavage occurs via the hole coupled C-H bond cleavage pathway followed by a radical mediated C-H cleavage to the C3H6 product. An exceptional selectivity of ∼90% for C3H6 production is achieved at about 13% propane conversion. The mechanistic model constructed in this study not only advances our understanding of C-H bond activation but also provides a new pathway for highly selective ODHP into C3H6 under mild conditions.

Low-Temperature C-H Bond Activation via Photocatalysis: Highly Efficient Ethylbenzene Dehydrogenation into Styrene on Rutile TiO2(110).

The direct dehydrogenation of hydrocarbons to olefins under mild conditions is an atom-economical but challenging route. Here, we have investigated photocatalytic ethylbenzene dehydrogenation into styrene on rutile(R)-TiO2(110) using the temperature-programmed desorption (TPD) method. The results demonstrate that photocatalytic ethylbenzene dehydrogenation into styrene occurs on R-TiO2(110) in a stepwise manner, in which the initial α-C-H bond cleavage occurs facilely under UV irradiation via a possible homolytic hydrogen atom transfer process and then is followed by the second C-H bond cleavage induced by either photocatalysis at ∼120 K or thermocatalysis at >400 K. With preadsorbed oxygen atoms to eliminate hydrogen atoms from ethylbenzene dehydrogenation and excess electrons on the surface, the yield of styrene is largely enhanced by about 4 times. The results not only demonstrate a photocatalytic route for ethylbenzene dehydrogenation into styrene on R-TiO2(110) but also advance our understanding of the photocatalytic activation of the saturated C-H bond with TiO2.