Metal stearate‐stabilized Cu nanoparticles, synthesized by an efficient one‐step process, were applied in the continuous liquid‐phase synthesis of methanol. After optimizing the reduction procedure, twofold higher rates of methanol formation were found for Cu–Zn colloids, compared to the conventional ternary Cu/ZnO/Al2O3 catalyst applied as fine powder in the liquid phase. Structural changes were investigated as a function of time on stream; after reduction in H2, spherical, well‐separated 5–10 nm Cu particles stabilized by a Zn stearate shell were found. Under catalytic high‐pressure conditions Zn stearate was hydrolyzed forming ZnO. High‐resolution transmission electron microscopy revealed the presence of triangular ZnO prisms with truncated edges. Applying optimized synthesis conditions these triangularly shaped ZnO particles were found to be mostly attached to the spherical Cu particles. The catalytic results and the structural and spectroscopic characterization suggest that these ZnO particles act as a reservoir, releasing ZnOx species, which diffuse onto the Cu particles and promote the catalytic activity.
A highly efficient one-step process to generate Cu-Zn colloids was developed, in which the colloidal particles were synthesized from Cu and Zn stearates by reduction with H(2) in a continuously operated stirred tank reactor. The resulting spherical, well separated particles have a size of 5-10 nm, consisting of a crystalline Cu(0) core (fcc) stabilized by a Zn stearate shell without long-range order. In situ attenuated total reflection FTIR spectroscopy was used to monitor the shift of the C-O stretching vibration of adsorbed CO as a function of temperature and pressure. The absence of the CO rotation-vibration bands of dissolved CO allowed us to obtain FTIR spectra at a CO pressure of 1.0 MPa at 473 K resulting in three shifted CO bands at 2030-2025, 1979-1978, and 1920 cm(-1). These bands indicate the presence of reduced coadsorbed Zn species on the metallic Cu surface. Cyclic CO adsorption experiments demonstrated the dynamics of the interaction between the Cu core and the Zn stearate shell.
The remarkably distinct reactivity of hydridozinc heterobimetallic cubanes [(HZnOtBu)4-n(thf LiOtBu)n] 1a-1d towards CO2 is reported--the hydride transfer from Zn-H to CO2 is drastically accelerated in the presence of Li ions in 1b-1d which led to the respective metal formate hydrates; the systems are inspiring models for the selective conversion of water gas into formates on lithium-promoted ZnO supports.
CO adsorption at 1 MPa on Cu-Zn stearate colloids and supported Cu catalysts was studied in situ by attenuated total reflection infrared (ATR-IR) spectroscopy. Subsequent to thorough reduction by H(2), the IR band at 2110-2070 cm(-1) due to linearly adsorbed CO on clean metallic Cu was always observed initially on all Cu catalysts. During the exposure of Zn-containing samples to CO at high pressure, a new IR band at ca. 1975 cm(-1) appeared in addition and increased in intensity even at room temperature. The detailed analysis of the IR spectra showed that the new IR band at ca. 1975 cm(-1) was not related to coadsorbed carbonate/formate-like species, but to the content of Zn in the samples. This IR band was found to be more stable than that at 2110-2070 cm(-1) during purging with inert gas. It disappeared quickly in synthetic air, pointing to a strongly reduced state of the Zn-containing Cu catalysts achieved during high-pressure CO exposure. It is suggested that CO can reduce ZnO to Zn in the presence of Cu, resulting in the formation of a CuZn(x) surface alloy. As the CO species with the characteristic IR band at ca. 1975 cm(-1) binds more strongly to this CuZn(x) alloy than the linearly adsorbed CO to pure Cu, it is suggested to be adsorbed on a bridge site.
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