Journal
INORGANIC CHEMISTRY
Volume 60, Issue 8, Pages 5573-5589Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.0c03467
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Funding
- Lawrence Technological University
- University of New Haven
- Higasket research fund
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The study found that [Cu(NH3)4(OH2)]SO4 could catalyze the formation of urea from ammonium carbamate in an aqueous solution, achieving a urea yield of 18%. A precipitation method using CO2 was developed to recover and reuse 66% of Cu(II), and the catalysis mechanism was investigated using density functional theory analysis.
The synthesis of urea fertilizer is currently the largest CO2 conversion process by volume in the industry. In this process, ammonium carbamate is an intermediate en route to urea formation. We determined that the tetraammineaquacopper(II) sulfate complex, [Cu(NH3)(4)(OH2)]SO4, catalyzed the formation of urea from ammonium carbamate in an aqueous solution. A urea yield of up to 18 +/- 6% was obtained at 120 degrees C after 15 h and in a high-pressure metal reactor. No significant urea formed without the catalyst. The urea product was characterized by Fourier transform infrared (FT-IR), powder X-ray diffraction (PXRD), and quantitative H-1{C-13} NMR analyses. The [Cu(NH3)(4)(OH2)]SO4 catalyst was then recovered at the end of the reaction in a 29% recovery yield, as verified by FT-IR, PXRD, and quantitative UV-vis spectroscopy. A precipitation method using CO2 was developed to recover and reuse 66 +/- 3% of Cu(II). The catalysis mechanism was investigated by the density functional theory at the B3LYP/6-31G** level with an SMD continuum solvent model. We determined that the [Cu(NH3)(4)](2+) complex is likely an effective catalyst structure. The study of the catalysis mechanism suggests that the coordinated carbamate with [Cu(NH3)(4)](2+) is likely the starting point of the catalyzed reaction, and carbamic acid can be involved as a transient intermediate that facilitates the removal of an OH group. Our work has paved the way for the rational design of catalysts for urea synthesis from the greenhouse gas CO2.
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