Xiao-Nan Wu

C–H Bond Activation by Oxygen-Centered Radicals over Atomic Clusters

Saturated hydrocarbons, or alkanes, are major constituents of natural gas and oil. Directly transforming alkanes into more complex organic compounds is a value-adding process, but the task is very difficult to achieve, especially at low temperature. Alkanes can react at high temperature, but these reactions (with oxygen, for example) are difficult to control and usually proceed to carbon dioxide and water, the thermodynamically stable byproducts. Consequently, a great deal of research effort has been focused on generating and studying chemical entities that are able to react with alkanes or efficiently activate C-H bonds at lower temperatures, preferably room temperature. To identify low-temperature methods of C-H bond activation, researchers have investigated free radicals, that is, species with open-shell electronic structures. Oxygen-centered radicals are typical of the open-shell species that naturally occur in atmospheric, chemical, and biological systems. In this Account, we survey atomic clusters that contain oxygen-centered radicals (O(-•)), with an emphasis on radical generation and reaction with alkanes near room temperature. Atomic clusters are an intermediate state of matter, situated between isolated atoms and condensed-phase materials. Atomic clusters containing the O(-•) moiety have generated promising results for low-temperature C-H bond activation. After a brief introduction to the experimental methods and the compositions of atomic clusters that contain O(-•) radicals, we focus on two important factors that can dramatically influence C-H bond activation. The first factor is spin. The O(-•)-containing clusters have unpaired spin density distributions over the oxygen atoms. We show that the nature of the unpaired spin density distribution, such as localization and delocalization within the clusters, heavily influences the reactivity of O(-•) radicals in C-H bond activation. The second factor is charge. The O(-•)-containing clusters can be negatively charged, positively charged, or neutral overall. We discuss how the charge state may influence C-H bond activation. Moreover, for a given charge state, such as the cationic state, it can be demonstrated that local charge distribution around the O(-•) centers can also significantly change the reactivity in C-H bond activation. Through judicious synthetic choices, spin and charge can be readily controllable physical quantities in atomic clusters. The adjustment of these two properties can impact C-H bond activation, thus constituting an important consideration in the rational design of catalysts for practical alkane transformations.

Characterization and reactivity of oxygen-centred radicals over transition metal oxide clusters

We introduce chemical structures and reactivity of oxygen-centred radicals (O(-)˙) over transition metal oxide (TMO) clusters based on mass spectrometric and density functional theory studies. Two main issues will be discussed: (1) the compositions of TMO clusters that have the bonding characteristics of (or contain) the O(-)˙ radicals; and (2) the dependences (cluster structures, sizes, charge states, metal types, etc.) of the chemical reactivity and selectivity for the O(-)˙ radicals over TMO clusters. One of the goals of cluster chemistry is to understand the elementary reactions involved with complex heterogeneous catalysis. The study of the O(-)˙ containing TMO clusters permits rather detailed descriptions for how mono-nuclear oxygen-centred radicals may exist and react with small molecules over TMO based catalysts.

Active Sites of Stoichiometric Cerium Oxide Cations (CemO2m+) Probed by Reactions with Carbon Monoxide and Small Hydrocarbon Molecules

Cerium oxide cluster cations (Ce(m)O(n)(+), m = 2-16; n = 2m, 2m +/- 1 and 2m +/- 2) are prepared by laser ablation and reacted with carbon monoxide (CO) and small hydrocarbon molecules (CH(4), C(2)H(4), and C(2)H(6)) in a fast flow reactor. A time of flight mass spectrometer is used to detect the cluster distribution before and after the reactions. The observation of oxygen reduction and hydrogen pickup of Ce(m)O(2m)(+) clusters strongly suggests the following reactions: (1) Ce(m)O(2m)(+) + C(2)H(4) --> Ce(m)O(2m-1)(+) + C(2)H(4)O (m = 2-6); (2) Ce(m)O(2m)(+) + CO --> Ce(m)O(2m-1)(+) + CO(2) (m = 4-6); and (3) Ce(m)O(2m)(+) + CH(4)/C(2)H(6) --> Ce(m)O(2m)H(+) + CH(3)/C(2)H(5) (m = 2-4). Density functional theory (DFT) calculations are performed to study reaction mechanisms of Ce(2)O(4)(+) + X (X = CO, CH(4), C(2)H(4), and C(2)H(6)). The calculated results are in good agreement with the experimental observations. The structural and bonding properties of Ce(m)O(2m)(+) (m = 2-5) clusters are also investigated by the DFT calculations. The unpaired electron in each of the clusters is mainly distributed over one Ce atom (4f and 5p orbitals) and two O atoms (2p orbital) in a CeO(2) moiety, which can be considered as the active site in the cluster. To further understand the nature of the active sites in Ce(m)O(2m)(+) clusters, the fast flow reaction experiments are also carried out on zirconium oxide clusters Zr(m)O(n)(+), because both Zr ([Kr]4d(2)5s(2)) and Ce ([Xe]4f(1)5d(1)6s(2)) have the same number of valence electrons while the latter has one more f and one less d electrons. In addition to the oxygen transfer reactions such as Zr(m)O(2m)(+) + C(2)H(4) --> Zr(m)O(2m-1)(+) + C(2)H(4)O (m = 1-4) reported in the literature, hydrogen abstraction reactions Zr(m)O(2m)(+) + CH(4)/C(2)H(6) --> Zr(m)O(2m)H(+) + CH(3)/C(2)H(5) are also identified. The rate constants of CO oxidation as well as hydrogen abstraction by Ce(m)O(2m)(+) and Zr(m)O(2m)(+) are very different. The reactivity and selectivity of Ce(m)O(2m)(+) versus Zr(m)O(2m)(+) can be well rationalized based on the DFT calculations. The oxygen transfer and hydrogen abstraction reactions studied in this work are of widespread importance. The nature of the active sites of Ce(m)O(2m)(+) clusters is unique and may be considered in the use and design of cerium oxide based catalysts.

Hydrogen-atom abstraction from methane by stoichiometric early transition metal oxide cluster cations

Stoichiometric early transition metal oxide cations (TiO(2))(1-5)(+), (ZrO(2))(1-4)(+), (HfO(2))(1-2)(+), (V(2)O(5))(1-5)(+), (Nb(2)O(5))(1-3)(+), (Ta(2)O(5))(1-2)(+), (MoO(3))(1-2)(+), (WO(3))(1-3)(+), and Re(2)O(7)(+) are able to activate the C-H bond of methane under near room temperature conditions.

Hydrogen-atom abstraction from methane by stoichiometric vanadium-silicon heteronuclear oxide cluster cations.

Vanadium-silicon heteronuclear oxide cluster cations were prepared by laser ablation of a V/Si mixed sample in an O(2) background. Reactions of the heteronuclear oxide cations with methane in a fast-flow reactor were studied with a time-of-flight (TOF) mass spectrometer to detect the cluster distribution before and after the reactions. Hydrogen abstraction reactions were identified over stoichiometric cluster cations [(V(2)O(5))(n)(SiO(2))(m)](+) (n=1, m=1-4; n=2, m=1), and the estimated first-order rate constants for the reactions were close to that of the homonuclear oxide cluster V(4)O(10) (+) with methane. Density functional calculations were performed to study the structural, bonding, electronic, and reactivity properties of these stoichiometric oxide clusters. Terminal-oxygen-centered radicals (O(t)*) were found in all of the stable isomers. These O(t)* radicals are active sites of the clusters in reaction with CH(4). The O(t)* radicals in [V(2)O(5)(SiO(2))(1-4)](+) clusters are bonded with Si rather than V atoms. All the hydrogen abstraction reactions are favorable both thermodynamically and kinetically. This work reveals the unique properties of metal/nonmetal heteronuclear oxide clusters, and may provide new insights into CH(4) activation on silica-supported vanadium oxide catalysts.

Methane activation by V3PO10˙+ and V4O10˙+ clusters: A comparative study

A series of vanadium and phosphorus heteronuclear oxide cluster cations (V(x)P(y)O(z)(+)) are prepared by laser ablation and the reactions of V(3)PO(10)˙(+) and V(4)O(10)˙(+) with methane in a fast flow reactor under the same conditions are studied. A time of flight mass spectrometer is used to detect the cluster distribution before and after reactions. In addition to previously identified reaction of V(4)O(10)˙(+) + CH(4)→ V(4)O(10)H(+) + CH(3)˙, the observation of hydrogen atom pickup cluster V(3)PO(10)H(+) suggests the reaction: V(3)PO(10)˙(+) + CH(4)→ V(3)PO(10)H(+) + CH(3)˙. The rate of the reaction of V(4)O(10)˙(+) with CH(4) is approximately 2.5 times faster than that of V(3)PO(10)˙(+) with CH(4). Density functional theory (DFT) calculations predict that structure of V(3)PO(10)˙(+) is topologically similar to that of V(4)O(10)˙(+), as well as that of P(4)O(10)˙(+), which is very similar to V(4)O(10)˙(+) in terms of methane activation in previous studies. The facile methane activation by the homo- and hetero-nuclear oxide clusters can all be attributed to the presence of an oxygen-centered radical (O˙) in these clusters. Further theoretical study indicates that the O˙ radical (or spin density of the cluster) can transfer within the high symmetry V(4)O(10)˙(+) and P(4)O(10)˙(+) clusters quite easily, and CH(4) molecule further enhances the rate of intra-cluster spin density transfer. In contrast, the intra-cluster spin density transfer within low symmetry V(3)PO(10)˙(+) is thermodynamically forbidden. The experimentally observed reactivity difference is consistent with the theoretical consideration of the intra-cluster spin density transfer.

Methane Activation by Yttrium‐Doped Vanadium Oxide Cluster Cations: Local Charge Effects

Methane activation, involved in the transformation of cheap and abundant natural gas into more valuable organic compounds, is a holy grail in chemistry, and has been studied for decades. Hydrogen atom abstraction (HAA) from CH4 to produce CH3C radicals is considered to be the decisive step in the oxidative dehydrogenation and dimerization of methane. Many metal and nonmetal oxide cluster cations that contain oxygen-centered radicals (O C) as active sites can react with CH4 to generate CH3C under thermal collision conditions. The O C-containing oxide anions usually have lower reactivity than the corresponding cations and can abstract a hydrogen atom only from more reactive alkanes such as ethane or butane. The charged states (cationic versus anionic) can thus significantly influence cluster reactivity. Herein, the experimental and computational studies demonstrate that for a certain charge state, that is the cationic state, the local charge distribution around the O C centers can also change the cluster reactivity toward methane dramatically. Such local charge effects on methane activation can generally exist in other related reaction systems, thus giving an important clue about designing efficient catalysts for methane transformation in practice. To demonstrate the local charge effects on methane activation, heteronuclear oxide clusters, namely, the yttriumdoped vanadium oxide cluster cations, are produced by laser ablation and treated with methane in a fast flow reactor under near-room-temperature-conditions. Methane activation by the V O C centers over pure vanadium oxide cluster cations including V4O10 + [3d] and a few others has been reported. The doping of other metals with a different number of valence electrons and electronegativity from those of vanadium may change the local charge distribution around the V O C centers significantly. Figure S1 (in the Supporting Information) shows that bimetallic V–Y clusters, along with pure V and Y oxide clusters, can be generated. The mass spectra in Figure 1 indicate that V4O10H + , V3YO9H + , and V2Y2O8H + (and the deuterated compounds) are produced upon the cluster reaction with CH4 (and CD4). It suggests that HAA takes place as follows:

CH Activation on Aluminum–Vanadium Bimetallic Oxide Cluster Anions

Aluminum-vanadium bimetallic oxide cluster anions (BMOCAs) have been prepared by laser ablation and reacted with ethane and n-butane in a fast-flow reactor. A time-of-flight mass spectrometer was used to detect the cluster distribution before and after the reactions. The observation of hydrogen-containing products AlVO(5)H(-) and Al(x)V(4-x)O(11-x)H(-) (x=1-3) strongly suggests that AlVO(5)(-) and Al(x)V(4-x)O(11-x)(-) (x=1-3) can react with ethane and n-butane by means of an oxidative dehydrogenation process at room temperature. Density functional theory studies have been carried out to investigate the structural, bonding, electronic, and reactive properties of these BMOCAs. Terminal-oxygen-centered radicals (O(t)(.)) were found in all of the reactive clusters, and the O(t)(.) atoms, which prefer to be bonded with Al rather than V atoms, are the active sites of these clusters. All the hydrogen-abstraction reactions are favorable both thermodynamically and kinetically. To the best of our knowledge, this is the first example of hydrogen-atom abstraction by BMOCAs and may shed light on understanding the mechanisms of C−−H activation on the surface of alumina-supported vanadia catalysts.

Reactivity of Atomic Oxygen Radical Anions Bound to Titania and Zirconia Nanoparticles in the Gas Phase: Low-Temperature Oxidation of Carbon Monoxide

Titanium and zirconium oxide cluster anions with dimensions up to nanosize are prepared by laser ablation and reacted with carbon monoxide in a fast low reactor. The cluster reactions are characterized by time-of-flight mass spectrometry and density functional theory calculations. The oxygen atom transfers from (TiO(2))(n)O(-) (n = 3-25) to CO and formations of (TiO(2))(n)(-) are observed, whereas the reactions of (ZrO(2))(n)O(-) (n = 3-25) with CO generate the CO addition products (ZrO(2))(n)OCO(-), which lose CO(2) upon the collisions (studied for n = 3-9) with a crossed helium beam. The computational study indicates that the (MO(2))(n)O(-) (M = Ti, Zr; n = 3-8) clusters are atomic radical anion (O(-)) bonded systems, and the energetics for CO oxidation by the O(-) radicals to form CO(2) is strongly dependent on the metals as well as the cluster size for the titanium system. Atomic oxygen radical anions are important reactive intermediates, while it is difficult to capture and characterize them for condensed phase systems. The reactivity pattern of the O(-)-bonded (TiO(2))(n)O(-) and (ZrO(2))(n)O(-) correlates very well with different behaviors of titania and zirconia supports in the low-temperature catalytic CO oxidation.

Collision-Induced Dissociation and Density Functional Theory Studies of CO Adsorption over Zirconium Oxide Cluster Ions: Oxidative and Nonoxidative Adsorption

Zirconium oxide cluster cations and anions are produced by laser ablation and reacted with CO in a fast flow reactor. The CO adsorption products Zr(x)O(y)CO(+) are observed for most of the generated cationic clusters (Zr(x)O(y)(+) = Zr(2)O(5,6)(+), Zr(3)O(7,8)(+), Zr(4)O(9,10)(+)...) while only specific anionic systems (Zr(x)O(y)(-) = Zr(3)O(7)(-), Zr(4)O(9)(-)...) absorb CO to produce Zr(x)O(y)CO(-). To study how the CO molecule is adsorbed on the clusters, the Zr(x)O(y)CO(±) products are mass-selected by a time-of-flight mass spectrometer (TOF-MS) and collided with a crossed helium beam. The fragment ions from collision-induced dissociation (CID) are detected by a secondary TOF-MS. Loss of CO and CO(2) is observed upon the collision of the helium beam with Zr(x)O(y)CO(+) and Zr(x)O(2x+1)CO(-), respectively. Density functional theory calculations indicate that oxidative and nonoxidative adsorption of CO takes place over Zr(3)O(7)(-) and Zr(3)O(7)(+), respectively. This is consistent with the CID experiments.