In catalysts for CO 2 hydrogenation, the interface between metal nanoparticles (NPs) and the support material is of high importance for the activity and reaction selectivity. In Pt NP-containing UiO Zr-metal–organic frameworks (MOFs), key intermediates in methanol formation are adsorbed at open Zr-sites at the Pt–MOF interface. In this study, we investigate the dynamic role of the Zr-node and the influence of H 2 O on the CO 2 hydrogenation reaction at 170 °C, through steady state and transient isotope exchange experiments, H 2 O cofeed measurements, and density functional theory (DFT) calculations. The study revealed that an increased number of Zr-node defects increase the formation rates to both methanol and methane. Transient experiments linked the increase to a higher number of surface intermediates for both products. Experiments involving either dehydrated or prehydrated Zr-nodes showed higher methanol and methane formation rates over the dehydrated Zr-node. Transient experiments suggested that the difference is related to competitive adsorption between methanol and water. DFT calculations and microkinetic modeling support this conclusion and give further insight into the equilibria involved in the competitive adsorption process. The calculations revealed weaker adsorption of methanol in defective or dehydrated nodes, in agreement with the larger gas phase concentration of methanol observed experimentally. The microkinetic model shows that [Zr 2 (μ-O) 2 ] 4+ and [Zr 2 (μ–OH)(μ-O)(OH)(H 2 O)] 4+ are the main surface species when the concentration of water is lower than the number of defect sites. Lastly, although addition of water was found to promote methanol desorption, water does not change the methanol steady state reaction rate, while it has a substantial inhibiting effect on CH 4 formation. These results indicate that water can be used to increase the reaction selectivity to methanol and encourages further detailed investigations of the catalyst system.
The mixed-anion compound with composition Sr2VO3Cl has been synthesized for the first time, using the conventional high-temperature solid-state synthesis technique in a closed silica ampule under inert conditions. This compound belongs to the known Sr2 TmO3Cl (Tm = Sc, Mn, Fe, Co, Ni) family, but with Tm = V. All homologues within this family can be described with the tetragonal space group P4/nmm (No. 129); from a Rietveld refinement of powder X-ray diffraction data on the Tm = V homologue, the unit cell parameters were determined to a = 3.95974(8) and c = 14.0660(4) Å, and the atomic parameters in the crystal structure could be estimated. The synthesized powder is black, implying that the compound is a semiconductor. The magnetic investigations suggest that Sr2VO3Cl is a paramagnet at high temperatures, exhibiting a μeff = 2.0 μB V–1 and antiferromagnetic (AFM) interactions between the magnetic vanadium spins (θCW = −50 K), in line with the V–O–V advantageous super-exchange paths in the V–O layers. Specific heat capacity studies indicate two small anomalies around 5 and 35 K, which however are not associated with long-range magnetic ordering. 35Cl ss-NMR investigations suggest a slow spin freezing below 4.2 K resulting in a glassy-like spin ground state.
The oxychloride SrTe 2 FeO 6 Cl is obtained by hightemperature solid-state synthesis under inert conditions in closed reaction vessels. The compound crystallizes in a novel monoclinic crystal structure that is described in the space group P12 1 /n1 (No. 14). The unit cell parameters, a = 10.2604(1) Å, b = 5.34556(5) Å, c = 26.6851(3) Å, and β = 93.6853(4)°, and atomic parameters were determined from synchrotron diffraction data, starting from a model that was obtained from single-crystal X-ray diffraction data. The anion lattice exhibits a rare ordering of oxide and chloride ions: onedimensional zig-zag ladders of chlorine (squarelike motif) are surrounded by an oxygen matrix. Two different iron sites coordinated solely to oxygen are present in the structure, one octahedral and one square pyramidal, both distorted. Similarly, two different strontium coordinations are present; the first homoleptic coordinated to eight oxygen atoms and the second heteroleptic coordinated to four oxygen and four chlorine atoms in a fac-like manner. The lone pair of Te(IV) is directed toward the larger chlorine atoms. Magnetic susceptibility measurements confirm that Fe is +3 (d 5 ) in the highspin electronic configuration, exhibiting an almost ideal spin-only moment, μ eff = 5.65 μ B Fe −1 . The slightly negative Weiss constant (θ CW = −39 K) suggests dominating antiparallel spin-to-spin coupling in the paramagnetic temperature range, agreeing with an observed long-range antiferromagnetic spin ordering below Neél temperature, T N ∼ 13 K, and a broad second order-like anomaly in the specific heat measurement data. Low-temperature neutron diffraction data reveal that the antiferromagnetic ordered phase is Ctype, with a k-vector (1/2, 1/2, 0) and ordered moment of 4.14(7) μ B . The spin structure can be described as antiferromagnetic ordered layers stacked along the a-axis, forming layers of squares that alternate along the c-axis.
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