Machine Learning for Experimental Reactivity of a Set of Metal Clusters toward C-H Activation.

Understanding the mechanisms of C-H activation of alkanes is a very important research topic. The reactions of metal clusters with alkanes have been extensively studied to reveal the electronic features governing C-H activation, while the experimental cluster reactivity was qualitatively interpreted case by case in the literature. Herein, we prepared and mass-selected over 100 rhodium-based clusters (RhxVyOz- and RhxCoyOz-) to react with light alkanes, enabling the determination of reaction rate constants spanning six orders of magnitude. A satisfactory model being able to quantitatively describe the rate data in terms of multiple cluster electronic features (average electron occupancy of valence s orbitals, the minimum natural charge on the metal atom, cluster polarizability, and energy gap involved in the agostic interaction) has been constructed through a machine learning approach. This study demonstrates that the general mechanisms governing the very important process of C-H activation by diverse metal centers can be discovered by interpreting experimental data with artificial intelligence.

Pyrolysis of mass-selected (V2O5)NO- (N = 1-6) clusters in a high-temperature linear ion trap reactor.

A high-temperature linear ion trap that can stably run up to 873 K was newly designed and installed into a homemade reflectron time-of-flight mass spectrometer coupled with a laser ablation cluster source and a quadrupole mass filter. The instrument was used to study the pyrolysis behavior of mass-selected (V2O5)NO- (N = 1-6) cluster anions and the dissociation channels were clarified with atomistic precision. Similar to the dissociation behavior of the heated metal oxide cluster cations reported in literature, the desorption of either atomic oxygen atom or molecular O2 prevailed for the (V2O5)NO- clusters with N = 2-5 at 873 K. However, novel dissociation channels involving fragmentation of (V2O5)NO- to small-sized VxOy - anions concurrent with the release of neutral vanadium oxide species were identified for the clusters with N = 3-6. Significant variations in branching ratios for different dissociation channels were observed as a function of cluster size. Kinetic studies indicated that the dissociation rates of (V2O5)NO- monotonically increased with the increase in cluster size. The internal energies carried by the (V2O5)NO- clusters at 873 K as well as the energetics data for dissociation channels have been theoretically calculated to rationalize the experimental observations. The decomposition behavior of vanadium oxide clusters from this study can provide new insights into the pyrolysis mechanism of metal oxide nanoparticles that are widely used in high temperature catalysis.

Rhodium chemistry: A gas phase cluster study.

Due to the extraordinary catalytic activity in redox reactions, the noble metal, rhodium, has substantial industrial and laboratory applications in the production of value-added chemicals, synthesis of biomedicine, removal of automotive exhaust gas, and so on. The main drawback of rhodium catalysts is its high-cost, so it is of great importance to maximize the atomic efficiency of the precious metal by recognizing the structure-activity relationship of catalytically active sites and clarifying the root cause of the exceptional performance. This Perspective concerns the significant progress on the fundamental understanding of rhodium chemistry at a strictly molecular level by the joint experimental and computational study of the reactivity of isolated Rh-based gas phase clusters that can serve as ideal models for the active sites of condensed-phase catalysts. The substrates cover the important organic and inorganic molecules including CH4, CO, NO, N2, and H2. The electronic origin for the reactivity evolution of bare Rhx q clusters as a function of size is revealed. The doping effect and support effect as well as the synergistic effect among heteroatoms on the reactivity and product selectivity of Rh-containing species are discussed. The ingenious employment of diverse experimental techniques to assist the Rh1- and Rh2-doped clusters in catalyzing the challenging endothermic reactions is also emphasized. It turns out that the chemical behavior of Rh identified from the gas phase cluster study parallels the performance of condensed-phase rhodium catalysts. The mechanistic aspects derived from Rh-based cluster systems may provide new clues for the design of better performing rhodium catalysts including the single Rh atom catalysts.

Activation of Methane by Rhodium Clusters on a Model Support C20H10.

Supported metals represent an important family of catalysts for the transformation of the most stable alkane, methane, under mild conditions. Here, using state-of-the-art mass spectrometry coupled with a newly designed double ion trap reactor that can run at high temperatures, we successfully immobilize a series of Rhn- (n = 4-8) cluster anions on a model support C20H10. Reactivity measurements at room temperature identify a significantly enhanced performance of large-sized Rh7,8C20H10- toward methane activation compared to that of free Rh7,8-. The "support" acting as an "electron sponge" is emphasized as the key factor to improve the reactivity of large-sized clusters, for which the high electron-withdrawing capability of C20H10 dramatically shifts the active Rh atom from the apex position in free Rh7- to the edge position in "supported" Rh7- to enhance CH4 adsorption, while the flexibility of C20H10 to release electrons further promotes subsequent C-H activation. The Rh atoms in direct contact with the support serve as electron-relay stations for electron transfer between C20H10 and the active Rh atom. This work not only establishes a novel approach to prepare and measure the reactivity of "supported" metal clusters in isolated gas phase but provides useful atomic-scale insights for understanding the chemical behavior of carbon (e.g., graphene)-supported metals in heterogeneous catalysis.