Understanding the complexity of a catalyst synthesis: Co-precipitation of mixed Cu,Zn,Al hydroxycarbonate precursors for Cu/ZnO/Al₂O₃ catalysts investigated by titration experiments

Co-precipitation of Cu,Zn,(Al) precursor materials is the traditional way of synthesizing Cu/ZnO/(Al2O3) catalysts for industrial methanol synthesis. This process has been investigated by titration experiments of nitrate and formate solutions. It was found that the solidification of the single components proceeds sequentially in case of nitrates: Cu2+ is precipitated at pH 3 and Zn2+ (as well as Al3+) near pH 5. This behavior prevents a homogeneous distribution of all metal species in the initial precipitate upon gradual increase of pH and requires application of the constant pH micro-droplet method. This effect is less pronounced if formate instead of nitrate is used as counter ion. This can be explained by the strong modification of the hydrolysis chemistry of the metal ions due to the presence of formate anions, which act as ligands and buffer. A formate-derived Cu/ZnO/Al2O3 catalyst was more active in methanol synthesis compared to a nitrate-derived sample although the same crystallographic phases were present in the precursor after co-precipitation and ageing. The effect of precipitation temperature was studied for the binary CuZn nitrate model system. Increasing the temperature of co-precipitation above 50 °C leads to down-shift of the precipitation pH of Zn2+ by a full unit. Thus, in warm solutions more acidic conditions can be used for complete co-precipitation, while in cold solutions, some Zn2+ may remain dissolved in the mother liquor at the same precipitation pH. The higher limit of temperature is given by the tendency of the initial Cu precipitate towards formation of CuO by oxolation. On the basis of these considerations, the empirically determined optimal pH and temperature conditions of the industrially applied synthesis can be rationalized

Cu/ZnO Catalyst Preparation via Formate Precursors

Cu/ZnO/(Al2O3) catalysts are of major industrial interest as they have been successfully applied in methanol synthesis for over 40 years. Highly productive catalysts exhibit a homogeneous microstructure and an optimal dispersion of the active copper phase. During synthesis of the catalyst, the relevant precursor phase is a mixed metal hydroxy carbonate, zincian malachite [1], which is typically co-precipitated from nitrate solutions. As an alternative approach, we synthesized metal hydroxy formates with different Cu:Zn ratios and used them as precursors for Cu/ZnO catalysts, the major advantage being a nitrate-free “green” catalyst synthesis. In this work we present precursor preparation and characterization as well as first catalytic results and discuss the potential of this novel preparation route for methanol synthesis catalysts

Knowledge-based development of a nitrate-free synthesis route for Cu/ZnO methanol synthesis catalysts via formate precursors

High-performance Cu/ZnO/(Al2O3) methanol synthesis catalysts are conventionally prepared by co-precipitation from nitrate solutions and subsequent thermal treatment. A new synthesis route is presented, which is based on similar preparation steps and leads to active catalysts, but avoids nitrate contaminated waste water

Chemical Aspects of the Candidate Antiferromagnetic Topological Insulator MnBi₂Te₄

High-quality single crystals of MnBi 2 Te 4 are grown for the first time by slow cooling within a narrow range between the melting points of Bi 2 Te 3 (586 °C) and MnBi 2 Te 4 (600 °C). Single-crystal X-ray diffraction and electron microscopy reveal ubiquitous antisite defects in both cation sites and, possibly, Mn vacancies (Mn 0.85(3) Bi 2.10(3) Te 4 ). Thermochemical studies complemented with high-temperature X-ray diffraction establish a limited high-temperature range of phase stability and metastability at room temperature. Nevertheless, the synthesis of MnBi 2 Te 4 can be scaled-up as powders can be obtained at subsolidus temperatures and quenched at room temperature. Bulk samples exhibit long-range antiferromagnetic ordering below 24 K. The Mn(II) out-of-plane magnetic state is confirmed by the magnetization, X-ray photoemission, X-ray absorption, and linear dichroism measurements. The compound shows a metallic type of resistivity in the range 4.5-300 K and is an n-type conductor that reaches a thermoelectric figure of merit up to ZT = 0.17. Angle-resolved photoemission experiments show a surface state forming a gapped Dirac cone, thus strengthening MnBi 2 Te 4 as a promising candidate for the intrinsic magnetic topological insulator, in accordance with theoretical predictions. The developed synthetic protocols enable further experimental studies of a crossover between magnetic ordering and nontrivial topology in bulk MnBi 2 Te 4 . © 2019 American Chemical Society