Phosphorus modified onion-like carbon catalyzed methanol conversion to dimethoxymethane: The unique role of P–C species

One-step synthesis of dimethoxymethane (DMM) via selective oxidation of methanol under the catalysis of nanocarbon is a green and sustainable but challenging chemical process. In the present work, a series of phosphorus-modified onion-like carbon (POLC) is prepared, and they have shown high activity in methanol conversion to DMM reaction. The proposed POLC catalysts exhibit two kinds of P-containing species, and C-P species is proved as the key factor for ensuring high DMM formation rate via linking the chemical structure to the catalytic performance of the catalysts. A temperature-programmed desorption experiment of intermediate products formaldehyde (FA) reveals that the physical-chemical nature behind the promotion effect of C-P species is enhancing the adsorption ability of the catalyst to FA ensuring the subsequent condensation reactions to form DMM in high selectivity.