Metallic catalysts (Cu/ZnO) and pure metals (Co, Ni, and Ag) without any impurities are directly prepared by a novel formic acid-assisted solid-state method without further reduction. During the decomposition of metal-formic acid precursors at 523 K under argon, H-2 and CO are liberated and act in situ as reducing agents to obtain pure metals and metallic catalysts (C-argon). X-ray diffraction, X-ray photoelectron spectroscopy, energy-dispersive spectroscopy, and temperature-programmed reduction analysis reveal that the as-prepared catalyst C-argon without further reduction is converted into metallic Cu-0 and ZnO species. TPR analysis results, Fourier transform infrared analysis, and the thermal decomposition behavior in air illustrate that no amorphous carbon or carbonic residues are left in C-argon when formic acid is used as the chelating agent and reductant, because formic acid is the simplest organic acid. The as-prepared Cu/ZnO catalyst is tested for low-temperature methanol synthesis at 443 K from syngas containing CO2 and using ethanol as a solvent and catalyst; it exhibits much higher activity and methanol selectivity than catalysts prepared by conventional solid-state methods. (c) 2013 Elsevier Inc. All rights reserved.