Reverse water gas-shift reaction product driven dynamic activation of molybdenum nitride catalyst surface.

In heterogeneous catalysis catalyst activation is often observed during the reaction process, which is mostly attributed to the induction by reactants. In this work we report that surface structure of molybdenum nitride (MoNx) catalyst exhibits a high dependency on the partial pressure or concentration of reaction products i.e., CO and H2O in reverse water gas-shift reaction (RWGS) (CO2:H2 = 1:3) but not reactants of CO2 and H2. Molybdenum oxide (MoOx) overlayers formed by oxidation with H2O are observed at reaction pressure below 10 mbar or with low partial pressure of CO/H2O products, while CO-induced surface carbonization happens at reaction pressure above 100 mbar and with high partial pressure of CO/H2O products. The reaction products induce restructuring of MoNx surface into more active molybdenum carbide (MoCx) to increase the reaction rate and make for higher partial pressure CO, which in turn promote further surface carbonization of MoNx. We refer to this as the positive feedback between catalytic activity and catalyst activation in RWGS, which should be widely present in heterogeneous catalysis.

Water-assisted oxidative redispersion of Cu particles through formation of Cu hydroxide at room temperature.

Sintering of active metal species often happens during catalytic reactions, which requires redispersion in a reactive atmosphere at elevated temperatures to recover the activity. Herein, we report a simple method to redisperse sintered Cu catalysts via O2-H2O treatment at room temperature. In-situ spectroscopic characterizations reveal that H2O induces the formation of hydroxylated Cu species in humid O2, pushing surface diffusion of Cu atoms at room temperature. Further, surface OH groups formed on most hydroxylable support surfaces such as γ-Al2O3, SiO2, and CeO2 in the humid atmosphere help to pull the mobile Cu species and enhance Cu redispersion. Both pushing and pulling effects of gaseous H2O promote the structural transformation of Cu aggregates into highly dispersed Cu species at room temperature, which exhibit enhanced activity in reverse water gas shift and preferential oxidation of carbon monoxide reactions. These findings highlight the important role of H2O in the dynamic structure evolution of supported metal nanocatalysts and lay the foundation for the regeneration of sintered catalysts under mild conditions.

Confinement-Induced Indium Oxide Nanolayers Formed on Oxide Support for Enhanced CO2 Hydrogenation Reaction.

An enclosed nanospace often shows a significant confinement effect on chemistry within its inner cavity, while whether an open space can have this effect remains elusive. Here, we show that the open surface of TiO2 creates a confined environment for In2O3 which drives spontaneous transformation of free In2O3 nanoparticles in physical contact with TiO2 nanoparticles into In oxide (InOx) nanolayers covering onto the TiO2 surface during CO2 hydrogenation to CO. The formed InOx nanolayers are easy to create surface oxygen vacancies but are against over-reduction to metallic In in the H2-rich atmospheres, which thus show significantly enhanced activity and stability in comparison with the pure In2O3 catalyst. The formation of interfacial In-O-Ti bonding is identified to drive the In2O3 dispersion and stabilize the metastable InOx layers. The InOx overlayers with distinct chemistry from their free counterpart can be confined on various oxide surfaces, demonstrating the important confinement effect at oxide/oxide interfaces.

Enhanced Methanol Synthesis over Self-Limited ZnOx Overlayers on Cu Nanoparticles Formed via Gas-Phase Migration Route.

Supported metal catalysts are widely used for chemical conversion, in which construction of high density metal-oxide or oxide-metal interface is an important means to improve their reaction performance. Here, Cu@ZnOx encapsulation structure has been in situ constructed through gas-phase migration of Zn species from ZnO particles onto surface of Cu nanoparticles under CO2 hydrogenation atmosphere at 450 °C. The gas-phase deposition of Zn species onto the Cu surface and growth of ZnOx overlayer is self-limited under the high temperature and redox gas (CO2 /H2 ) conditions. Accordingly, high density ZnOx -Cu interface sites can be effectively tailored to have an enhanced activity in CO2 hydrogenation to methanol. This work reveals a new route for the construction of active oxide-metal interface and classic strong metal-support interaction state through gas-phase migration of support species induced by high temperature redox reaction atmosphere.

Spatially Separated Active Sites Enable Selective CO Oxidation Reaction on Oxide Catalyst.

The search for efficient non-noble-metal catalysts able to perform selective oxidation reactions is of great importance, with relevance to many catalytic processes. However, this is often hampered because the origin of the selectivity remains controversial, particularly for reactions catalyzed by oxides. Here, combining high-pressure surface imaging techniques and theoretical calculations, we identify that spatially separated active sites for O2 activation and H2 adsorption on an ultrathin Mn3O4 surface enable selective oxidation of CO over H2. Theoretical calculations reveal that Mn-O pairs for H2 dissociation are separated from Mn-Mn pairs for the formation of adsorbed O2* so that H2 has to surmount much higher barriers for both H2 dissociation and H diffusion while CO can directly react with O2* following the Eley-Rideal process. Our study sheds light on the atomic-level understanding of the surface structure-dependent selective oxidation reaction on oxide catalysts.

Disentangling Local Interfacial Confinement and Remote Spillover Effects in Oxide-Oxide Interactions.

Supported oxides are widely used in many important catalytic reactions, in which the interaction between the oxide catalyst and oxide support is critical but still remains elusive. Here, we construct a chemically bonded oxide-oxide interface by chemical deposition of Co3O4 onto ZnO powder (Co3O4/ZnO), in which complete reduction of Co3O4 to Co0 has been strongly impeded. It was revealed that the local interfacial confinement effect between Co oxide and the ZnO support helps to maintain a metastable CoOx state in CO2 hydrogenation reaction, producing 93% CO. In contrast, a physically contacted oxide-oxide interface was formed by mechanically mixing Co3O4 and ZnO powders (Co3O4-ZnO), in which reduction of Co3O4 to Co0 was significantly promoted, demonstrating a quick increase of CO2 conversion to 45% and a high selectivity toward CH4 (92%) in the CO2 hydrogenation reaction. This interface effect is ascribed to unusual remote spillover of dissociated hydrogen species from ZnO nanoparticles to the neighboring Co oxide nanoparticles. This work clearly illustrates the equally important but opposite local and remote effects at the oxide-oxide interfaces. The distinct oxide-oxide interactions contribute to many diverse interface phenomena in oxide-oxide catalytic systems.

Activating lattice oxygen of single-layer ZnO for the catalytic oxidation reaction.

Tuning an oxide/metal interface is of critical importance for the performance enhancement of many heterogeneous catalytic reactions. However, catalytic oxidation occurring at the interface between non-reducible oxide and metal has been challenging, since non-reducible oxides hardly lose their lattice oxygen (OL) or dissociate O2 from the gas phase. In this work, a ZnO monolayer film on Au(111) is used as an inverse catalyst to investigate CO oxidation occurring at the ZnO/Au(111) interface via high pressure scanning tunneling microscopy. Surface science experiments indicate that oxygen intercalation under the ZnO monolayer film, termed ZnO/O/Au(111), can be achieved via a surface reaction with 1 × 10-6 mbar O3. Subsequent exposure of the formed ZnO/O/Au(111) surface to mbar CO at room temperature leads to the recovery of the pristine ZnO/Au(111) surface. Theoretical calculations reveal that OL adjacent to intercalated oxygen (Oint) is activated due to the OL-Zn-Oint bonding and surface corrugation, which can be directly involved in CO oxidation. Subsequently, Oint migrates to the formed oxygen vacancy from the subsurface resuming the pristine ZnO structure. These results thus reveal that oxygen intercalation underneath single-layer ZnO will strongly boost the oxidation reaction via activating adjacent lattice oxygen atoms.

Direct observation of accelerating hydrogen spillover via surface-lattice-confinement effect.

Uncovering how hydrogen transfers and what factors control hydrogen conductivity on solid surface is essential for enhancing catalytic performance of H-involving reactions, which is however hampered due to the structural complexity of powder catalysts, in particular, for oxide catalysts. Here, we construct stripe-like MnO(001) and grid-like Mn3O4(001) monolayers on Pt(111) substrate and investigate hydrogen spillover atop. Atomic-scale visualization demonstrates that hydrogen species from Pt diffuse unidirectionally along the stripes on MnO(001), whereas it exhibits an isotropic pathway on Mn3O4(001). Dynamic surface imaging in H2 atmosphere reveals that hydrogen diffuses 4 times more rapidly on MnO than the case on Mn3O4, which is promoted by one-dimension surface-lattice-confinement effect. Theoretical calculations indicate that a uniform and medium O-O distance favors hydrogen diffusion while low-coordinate surface O atom inhibits it. Our work illustrates the surface-lattice-confinement effect of oxide catalysts on hydrogen spillover and provides a promising route to improve the hydrogen spillover efficiency.

Stabilizing Oxide Nanolayer via Interface Confinement and Surface Hydroxylation.

Surface hydroxylation over oxide catalysts often occurs in many catalytic processes involving H2 and H2O, which is considered to play an important role in elementary steps of the reactions. Here, monolayer CoO and CoOHx nanoislands on Pt(111) are used as inverse model catalysts to study the effect of surface hydroxylation on the stability of Co oxide overlayers in O2. Surface science experiments indicate that hydroxyl groups formed on CoO nanoislands produced by deuterium-spillover can enhance oxidation resistance of the Co oxide nanostructures. Theoretical calculation shows that the interfacial adhesion between CoO and Pt is linearly strengthened with the increasing hydroxylation degree of CoO surface. Thus, the interface confinement effect between CoO and Pt can be enhanced by the surface hydroxylation due to the more reduced Co ions and stronger Co-Pt bonding at the CoOHx/Pt interface.

Low-temperature growth of ultrathin and epitaxial Mo2C nanosheets via a vapor-liquid-solid process.

Due to the unique physical and chemical properties, transition metal carbides (TMCs) have many potential applications in the fields of energy conversion and catalysis. Chemical vapor deposition (CVD) is a promising method to synthesize TMCs. However, spatially inhomogeneous supply of transition metal precursor vapor in the normal CVD process generally leads to poor control of the morphology and uniformity of the products. Here, we report a vapor-liquid-solid (VLS) growth process where non-volatile Na2MoO4 is used to act as a liquid precursor for the growth of uniform ultrathin Mo2C nanosheets on Al2O3(0001). The morphology of the nanosheets can be controlled by tuning the precursor concentration, annealing time and growth temperature. The roles of Na and the liquid-solid interface in consolidating Mo atoms and promoting the epitaxial growth of Mo2C nanosheets are demonstrated. Furthermore, we show that the liquid-solid interface can cause the crystalline phase transition of Mo2C nanosheets through verification experiments.

Dynamic transformation between bilayer islands and dinuclear clusters of Cr oxide on Au(111) through environment and interface effects.

SignificanceFor oxide catalysts, it is important to elucidate and further control their atomic structures. In this work, well-defined CrO2 bilayer islands and Cr2O7 dinuclear clusters have been grown on Au(111) and unambiguously identified by scanning tunneling microscopy and theoretical calculations. Upon cycled redox treatments, the two kinds of oxide nanostructures can be reversibly transformed. It is interesting to note that both Cr oxides do not exist in bulk but need to be stabilized by the metal surface and the specific environment. Our results suggest that both redox atmosphere and interface confinement effects can be used to construct an oxide nanostructure with the specific chemical state and structure.

Overturning CO2 Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal-Support Interactions.

Encapsulation of metal nanoparticles by support-derived materials known as the classical strong metal-support interaction (SMSI) often happens upon thermal treatment of supported metal catalysts at high temperatures (≥500 °C) and consequently lowers the catalytic performance due to blockage of metal active sites. Here, we show that this SMSI state can be constructed in a Ru-MoO3 catalyst using CO2 hydrogenation reaction gas and at a low temperature of 250 °C, which favors the selective CO2 hydrogenation to CO. During the reaction, Ru nanoparticles facilitate reduction of MoO3 to generate active MoO3-x overlayers with oxygen vacancies, which migrate onto Ru nanoparticles' surface and form the encapsulated structure, that is, Ru@MoO3-x. The formed SMSI state changes 100% CH4 selectivity on fresh Ru particle surfaces to above 99.0% CO selectivity with excellent activity and long-term catalytic stability. The encapsulating oxide layers can be removed via O2 treatment, switching back completely to the methanation. This work suggests that the encapsulation of metal nanocatalysts can be dynamically generated in real reactions, which helps to gain the target products with high activity.

Oxidative Strong Metal-Support Interactions between Metals and Inert Boron Nitride.

The strong metal-support interaction (SMSI) is one of the most important concepts in heterogeneous catalysis, which has been widely investigated between metals and active oxides triggered by reductive atmospheres. Here, we report the oxidative strong metal-support interaction (O-SMSI) effect between Pt nanoparticles (NPs) and inert hexagonal boron nitride (h-BN) sheets, in which Pt NPs are encapsulated by oxidized boron (BOx) overlayers derived from the h-BN support under oxidative conditions. De-encapsulation of Pt NPs has been achieved by washing in water, and the residual ultrathin BOx overlayers work synergistically with surface Pt sites for enhancing CO oxidation reaction. The O-SMSI effect is also present in other h-BN-supported metal catalysts such as Au, Rh, Ru, and Ir within different oxidative atmospheres including O2 and CO2, which is determined by metal-boron interaction and O affinity of metals.

In situ identification of the metallic state of Ag nanoclusters in oxidative dispersion.

Oxidative dispersion has been widely used in regeneration of sintered metal catalysts and fabrication of single atom catalysts, which is attributed to an oxidation-induced dispersion mechanism. However, the interplay of gas-metal-support interaction in the dispersion processes, especially the gas-metal interaction has not been well illustrated. Here, we show dynamic dispersion of silver nanostructures on silicon nitride surface under reducing/oxidizing conditions and during carbon monoxide oxidation reaction. Utilizing environmental scanning (transmission) electron microscopy and near-ambient pressure photoelectron spectroscopy/photoemission electron microscopy, we unravel a new adsorption-induced dispersion mechanism in such a typical oxidative dispersion process. The strong gas-metal interaction achieved by chemisorption of oxygen on nearly-metallic silver nanoclusters is the internal driving force for dispersion. In situ observations show that the dispersed nearly-metallic silver nanoclusters are oxidized upon cooling in oxygen atmosphere, which could mislead to the understanding of oxidation-induced dispersion. We further understand the oxidative dispersion mechanism from the view of dynamic equilibrium taking temperature and gas pressure into account, which should be applied to many other metals such as gold, copper, palladium, etc. and other reaction conditions.

Design of Lewis Pairs via Interface Engineering of Oxide-Metal Composite Catalyst for Water Activation.

The rational design and controlled construction of active centers remain grand challenges in heterogeneous catalysis, in particular for oxide catalysts with complex surface and interface structures. This work describes a facile way in the design of highly active Ni-O Lewis pairs for water activation where Ni and O sites act as Lewis acid and base, respectively. Surface science experiments indicate that dissociative adsorption of water occurs at edges of NiOx nanoislands grown on Au(111) and NiOx-Ni interfaces formed by further depositing metallic Ni layers along the edges of NiOx nanoislands. Enhanced activity of Ni-O Lewis pairs at the NiOx-Ni interface has been demonstrated by theoretical calculations, which are attributed to the higher Lewis acidity of metallic Ni sites and synergy of the metal and oxide components. Moreover, proton can migrate away from the NiOx-Ni interface and refresh the O base sites, leading to further hydroxylation of the neighboring Ni acid sites.

Coverage-Dependent Behaviors of Vanadium Oxides for Chemical Looping Oxidative Dehydrogenation.

Chemical looping provides an energy- and cost-effective route for alkane utilization. However, there is considerable CO2 co-production caused by kinetically mismatched O2- bulk diffusion and surface reaction in current chemical looping oxidative dehydrogenation systems, rendering a decreased olefin productivity. Sub-monolayer or monolayer vanadia nanostructures are successfully constructed to suppress CO2 production in oxidative dehydrogenation of propane by evading the interference of O2- bulk diffusion (monolayer versus multi-layers). The highly dispersed vanadia nanostructures on titanium dioxide support showed over 90 % propylene selectivity at 500 °C, exhibiting turnover frequency of 1.9×10-2  s-1 , which is over 20 times greater than that of conventional crystalline V2 O5 . Combining in situ spectroscopic characterizations and DFT calculations, we reveal the loading-reaction barrier relationship through the vanadia/titanium interfacial interaction.

FeO6 Octahedral Distortion Activates Lattice Oxygen in Perovskite Ferrite for Methane Partial Oxidation Coupled with CO2 Splitting.

Modulating lattice oxygen in metal oxides that conducts partial oxidation of methane in balancing C-H activation and syngas selectivity remains challenging. This paper describes the discovery of distorting FeO6 octahedra in La1-xCexFeO3 (x = 0, 0.25 0.5, 0.75, 1) orthorhombic perovskites for the promotion of lattice oxygen activation. By combined electrical conductivity relaxation measurements and density functional theory calculations studies, this paper describes the enhancement of FeO6 octahedral distortion in La1-xCexFeO3 promoting their bulk oxygen mobility and surface oxygen exchange capability. Consequently, La0.5Ce0.5FeO3 with the highest FeO6 distortion achieves exceptional syngas productivity of ∼3 and 8 times higher than LaFeO3 and CeFeO3, respectively, in CH4 partial oxidation step with simultaneous high CO2 conversion (92%) in the CO2-splitting step at 850 °C. The results exemplify the feasibility to tailor the active lattice oxygen of perovskite by modulating the distortion of BO6 in ABO3, which ultimately influences their reaction performance in chemical looping processes.

Facilitating the reduction of V-O bonds on VO x /ZrO2 catalysts for non-oxidative propane dehydrogenation.

Supported vanadium oxide is a promising catalyst in propane dehydrogenation due to its competitive performance and low cost. Nevertheless, it remains a grand challenge to understand the structure-performance correlation due to the structural complexity of VO x -based catalysts in a reduced state. This paper describes the structure and catalytic properties of the VO x /ZrO2 catalyst. When using ZrO2 as the support, the catalyst shows six times higher turnover frequency (TOF) than using commercial γ-Al2O3. Combining H2-temperature programmed reduction, in situ Raman spectroscopy, X-ray photoelectron spectroscopy and theoretical studies, we find that the interaction between VO x and ZrO2 can facilitate the reduction of V-O bonds, including V[double bond, length as m-dash]O, V-O-V and V-O-Zr. The promoting effect could be attributed to the formation of low coordinated V species in VO x /ZrO2 which is more active in C-H activation. Our work provides a new insight into understanding the structure-performance correlation in VO x -based catalysts for non-oxidative propane dehydrogenation.

Modulating Lattice Oxygen in Dual-Functional Mo-V-O Mixed Oxides for Chemical Looping Oxidative Dehydrogenation.

Oxygen chemistry plays a pivotal role in numerous chemical reactions. In particular, selective cleavage of C-H bonds by metal oxo species is highly desirable in dehydrogenation of light alkanes. However, high selectivity of alkene is usually hampered through consecutive oxygenation reactions in a conventional oxidative dehydrogenation (ODH) scheme. Herein, we show that dual-functional Mo-V-O mixed oxides selectively convert propane to propylene via an alternative chemical looping oxidative dehydrogenation (CL-ODH) approach. At 500 °C, we obtain 89% propylene selectivity at 36% propane conversion over 100 dehydrogenation-regeneration cycles. We attribute such high propylene yield-which exceeds that of previously reported ODH catalysts-to the involvement and precise modulation of bulk lattice oxygen via atomic-scale doping of Mo and show that increasing the binding energy of V-O bonds is critical to enhance the selectivity of propylene. This work provides the fundamental understanding of metal-oxygen chemistry and a promising strategy for alkane dehydrogenation.

The Interplay between Structure and Product Selectivity of CO2 Hydrogenation.

Identification of the active structure under reaction conditions is of great importance for the rational design of heterogeneous catalysts. However, this is often hampered by their structural complexity. The interplay between the surface structure of Co3 O4 and the CO2 hydrogenation is described. Co3 O4 with morphology-dependent crystallographic surfaces presents different reducibility and formation energy of oxygen vacancies, thus resulting in distinct steady-state composition and product selectivity. Co3 O4 -0 h rhombic dodecahedra were completely reduced to Co0 and CoO, which presents circa 85 % CH4 selectivity. In contrast, Co3 O4 -2 h nanorods were partially reduced to CoO, which exhibits a circa 95 % CO selectivity. The crucial role of the Co3 O4 structure in determining the catalytic performance for higher alcohol synthesis over CuCo-based catalysts is demonstrated. As expected, Cu/Co3 O4 -2 h shows nine-fold higher ethanol yield than Cu/Co3 O4 -0 h owing to the inhibition for methanation.