Among them, Pt delivers the main carbonaceous liquid product of formamide while Ni and Fe mainly produce formic acid products (Supplementary Fig. After 3-h electrolysis, Pt, Ni, and Fe catalysts show the capacity for formamide formation, and their Faradaic efficiencies (FE formamide) are 11.70%, 7.31%, and 1.44% (Supplementary Fig. The carbonaceous liquid product was analyzed and quantified by 1H-nuclear magnetic resonance ( 1H-NMR, Supplementary Fig. The mixture of methanol and ammonia with a 2:1 volume ratio in 0.5 M NaHCO 3 aqueous solution was measured at the current density of 10 mA cm −2. A single cell can greatly reduce the operating cost compared with a membrane-separated two-chamber cell. Ten species of metal anode catalysts, including Pt, Ni, Fe, Cu, Al, Co, Ti, Pb, Mo, and W, were screened using the galvanostatic method. The conjecture of formamide electrosynthesis from methanol and ammonia oxidation is testified in a membrane-free single cell. Notably, the techno-economic analysis (TEA) proves the cost advantage of formamide electrosynthesis strategy over current industry manufacturing. Furthermore, a flow cell is adopted for continuous formamide electrosynthesis without performance decay in a 46-h stability test. Combining the computational study, the high formamide production efficiency is ascribed to the moderate binding affinity of the reaction intermediates on PtO 2, which is formed on the surface of the Pt electrocatalyst during the reaction. The key reaction intermediates are recognized by isotope-labeled in situ Attenuated Total Reflection Flourier Transformed Infrared Spectroscopy (ATR-FTIR) and online differential electrochemical mass spectrometry (DEMS). The optimized selectivity from methanol to formamide and Faradaic efficiency can reach 74.26% and 40.39% at 100 mA cm −2 current density in a single cell. Among all the screened electrocatalysts, Pt shows the highest performance. Herein, we demonstrate a methanol electrolysis approach to synthesize formamide in an aqueous ammonia medium at ambient temperature and pressure (Fig. Thus, the exploration of an alternative electrooxidation process using abundant carbon- and nitrogen-containing feedstocks to synthesize formamide under ambient conditions is attractive but remains a great challenge. But, the sluggish anodic oxygen evolution reaction requires a high applied potential. At present, these important advances mainly focused on the electrochemical reduction reactions to construct the C–N bond. For instance, the electrosynthesis of methylamine, formamide, and acetamide has been successfully achieved by using CO 2/CO as the carbon source 6, 7, 8, 10. The electrochemical technique, especially driven by renewable energy, has gained increasing attention for the synthesis of many high-valued chemicals 6, 7, 8, 9, 10, 11, 12, 13, 14. Searching for novel solutions that allow energy-efficient and green synthesis of formamide is significant. 1a) 5, which consumes huge fossil fuels and aggravates the greenhouse effect. Currently, formamide is produced through the reaction of carbon monoxide and ammonia under high-temperature and high-pressure conditions via the following two strategies (Eqs. Formamide alone has an annual global market of millions of tons 4. This work offers a way to synthesize formamide via C–N coupling and can be extended to substantially synthesize other value-added organonitrogen chemicals (e.g., acetamide, propenamide, formyl methylamine).Īmides, a very important class of compounds in chemistry and biology, have been studied extensively over the past century 1, 2, 3. The combined results of in situ experiments and theoretical simulations unveil the C–N bond formation mechanism via nucleophilic attack of NH 3 on an aldehyde-like intermediate derived from methanol electrooxidation. A 46-h continuous test performed in the flow cell shows no performance decay. Here we report a single-cell electrochemical oxidation approach to transform methanol and ammonia into formamide under ambient conditions over Pt electrocatalyst that provides 74.26% selectivity from methanol to formamide and a Faradaic efficiency of 40.39% at 100 mA cm −2 current density, gaining an economic advantage over conventional manufacturing based on techno-economic analysis. Electrochemical conversion of abundant carbon- and nitrogen-containing small molecules into high-valued organonitrogen compounds is alluring to reducing current dependence on fossil energy.
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