The nickel phosphides have garnered increasing attention as an excellent catalytic site in the fields of electrocatalysis and hydrotreating, but their application in organic synthesis remains infrequent. In this study, ammonium phosphate and nickel chloride were employed as the doping sources for the first time to synthesize the Ni-based ZIF-8 precursor via the host–guest method. Subsequently, the precursor was pyrolyzed to obtain Ni2P nanoparticles (NPs) supported on N, P co-doped carbon. The composite materials exhibit elevated metal loading and effective dispersion due to the synergistic combination of phosphorus and nickel. Specifically, compared with Ni-NC, the optimal Ni2P-NCP-1 exhibits enhanced catalytic activity in the α-alkylation of arylacetonitriles with alcohols using KOH as the base. It shows a wide broad substrate scope at 140 °C for 12 h in n-octane using a hydrogen borrowing strategy. Through characterizations and mechanistic studies, it has been discovered that the introduction of P source not only provides more basic sites on carbon matrix but also leads to the formation of Ni2P NPs, which facilitates the catalytic efficiency by modifying the electronic structure of Ni. Compared with the metallic Ni species, the synergistic effect between Ni2P and acid-basic sites significantly influences the dehydrogenation of alcohols to generate Ni–H species. This study successfully achieves simultaneous phosphating of both the metal and support, and it also demonstrates that the N2P-NCP-1 catalyst has significant potential in the heterogeneous organic transformation field.
Heteroatom doped carbon materials have attracted intense attention in constructing electrochemical sensors because of their outstanding electrocatalytic performance. Up to now, most of the researches were focused on the electrochemical application of single heteroatom doped carbon microspheres. In this work, N, P-co-doped carbon microspheres (NP-CMs) modified electrode was developed as highly sensitive electrochemical sensor for acetaminophen. NP-CMs were acquired by the calcination of products from the one-pot reaction of dopamine and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). Experimental results revealed that NP-CMs showed better electrocatalytic performance compared with N-doped carbon microspheres. Under the optimal conditions, the response of NP-CMs/GCE showed a linear relationship with acetaminophen concentration from 0.07 μM to 30 μM, the linear equation was Y = 0.01356X+0.7417 and the detection limit was 40 nM (S/N = 3). The recoveries of the NP-CMs modified GCE for the assay of acetaminophen in human serum samples were from 94.0% to 106.0%. It was believed that N, P-co-doped carbon microspheres have a great potential in the design of novel pharmaceutical analysis methods.
Aling Chen,Qingfeng Yi,Kuang Sheng,Yuebing Wang,Jiangchuan Chen,Qiaoli Zhang,Kaiwen Xiang,Guanghua Tan
Development of high-efficiency oxygen reduction reaction (ORR) catalysts under neutral conditions has made little research progress. In this work, we synthesized a three-dimensional porous N/P codoped carbon nanosheet composites (CNP@PNS) by high-temperature thermal treatment of dicyandiamide, starch, and triphenylphosphine and subsequent porous structure-making treatment using the NaCl molten salt template. In the neutral solution, the electrocatalytic performance of the CNP@PNS-4 catalyst exhibits an onset potential of 0.98 V (vs reversible hydrogen electrode) and a half-wave potential of 0.91 V for ORR, which greatly surpasses commercial Pt/C (40%). Three kinds of neutral metal–air batteries (Zn–air, Al–air, and Fe–air) using the prepared samples as cathodic catalysts were constructed, corresponding to the maximum power density of 120.2, 78.3, and 18.9 mW·cm–2, respectively. Also, they reveal outstanding discharge stability under different current densities. The density functional theory calculation depicts the reduction of the free energy of the determining step and subsequent decline of the overpotential for ORR.
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