CO₂ Activation and Hydrogenation by PtH_n⁻ Cluster Anions

Abstract

Gas phase reactions between PtHn− cluster anions and CO2 were investigated by mass spectrometry, anion photoelectron spectroscopy, and computations. Two major products, PtCO2H− and PtCO2H3−, were observed. The atomic connectivity in PtCO2H− can be depicted as HPtCO2−, where the platinum atom is bonded to a bent CO2 moiety on one side and a hydrogen atom on the other. The atomic connectivity of PtCO2H3− can be described as H2Pt(HCO2)−, where the platinum atom is bound to a formate moiety on one side and two hydrogen atoms on the other. Computational studies of the reaction pathway revealed that the hydrogenation of CO2 by PtH3− is highly energetically favorable.

Elucidating the Mechanism of Simultaneous Activation of CH4 and CO2 Mediated by Single Group 10 Metal Anions in Gas Phase

“…For example, 5d transition metals including Ta + /W + /Os + /Ir + /Pt + can dehydrogenate CH 4 to form metal‐carbene complex [M−CH 2 ] + ; [8–9] FeO + /CuO + can mediate hydrogen‐atom abstraction from CH 4 to generate CH 3 ⋅ or convert CH 4 into CH 3 OH; [10–14] Au/Cu carbides couple with CH 4 to generate C 2 H 4. [15–16] For the case of CO 2 activation, Sc + /Y + /La + /Ti + /Zr + /Hf + /Nb + /Ta + /W + and Mo/W oxide clusters can reduce CO 2 to CO through oxygen‐atom abstraction; [17–18] metal hydrides, FeH − /CoH − /CuH − /PtH 3 − , can convert CO 2 into hydrogenation product HCO 2 − through direct hydride transfer [19–21] . Nevertheless, the mutual transformation of both CH 4 and CO 2 that mediated by such ionic clusters are rare, where the limited examples are Ta + and CuB + couple CH 4 and CO 2 to produce ketene; [22–25] dinuclear clusters, RhVO 3 − and RhTiO 2 − , mediate the conversion of CH 4 and CO 2 to produce methanol and formaldehyde or syngas, respectively [26–27] …”

Giant NLO response and deep ultraviolet transparency of dual (alkali/alkaline earth) metals doped C6O6Li6 electrides

“…The large negative interaction energy reflects exothermicity of the reaction. Thermodynamic stability assures the experimental synthesis and practical application of a complex possible [ 60 ]. In this report, we also calculated the interaction energy of all complexes to estimate their thermal stability ( Table 1 ).…”

“…As discussed earlier, nonlinear optical materials having high β o are used in second harmonic generation for doubling of frequency [ 60 , 78 ]. To check the UV transparency of these electrides, we performed TD-DFT analysis of the isolated C 6 O 6 Li 6 and alk-C 6 O 6 Li 6 -alkearth electrides.…”