Porous Heteroatom‐Doped Carbons: Efficient Catalysts for Selective Oxidation of Alcohols by Activated Persulfate

Abstract

Aldehydes are essential chemicals for industrial feedstock. However, the traditional processes to produce these chemicals face many limitations, such as waste generation, low selectivity, or high cost. Herein, we report the synthesis and characterization of a group of porous heteroatom (P, B or N)-doped carbons and their use as catalysts for the oxidation of primary alcohols by activating peroxydisulfate. Among the heteroatom-doped carbons, porous N-doped carbons pyrolyzed at 700 or 800 °C show the highest activity. Experimental studies were performed suggesting a considerable contribution of a nonradical oxidation process. Furthermore, N-doped carbons can act as a catalyst in the oxidation of a large substrate scope of substituted alcohols.

Enhanced activation of persulfate improves the selective oxidation of alcohols catalyzed by earth-abundant metal oxides embedded on porous N-doped carbon derived from chitosan

“…The spectrum could be deconvoluted into four sub-peaks N pyridinic (398 eV), N pyrrolic (400.5 eV), N graphitic (402.4 eV), and N oxides (404.5 eV). 30 Fig. S4† shows the XPS analysis of C1s and O1s.…”

“…The spectrum could be deconvoluted into four sub-peaks N pyridinic (398 eV), N pyrrolic (400.5 eV), N graphitic (402.4 eV), and N oxides (404.5 eV). 30 The immobilization of metal species (nickel, cobalt, copper, or iron) was done by employing citric acid as a coordinating agent, followed by the formed complex interaction with CN-meso, solvent evaporation, and thermal treatment. In all cases, 5 wt% metal loading was incorporated into CN-meso.…”

“…[25][26][27] Recently, selective oxidation of aromatic alcohols via PMS or PDS activation was reported under metal-free conditions using doped carbons. [28][29][30] However, the metal-free carbon-mediated persulfate activation is commonly less efficient than with metal-containing catalysts. [31][32][33] Liu et al showed that cobalt single atoms embedded in nitrogen-doped graphene presented a three-fold increase in catalytic activity compared to N-doped graphene.…”

Cerium Oxide Nanoparticles Confined in Doped Mesoporous Carbons: A Strategy to Produce Catalysts for Imine Synthesis

“…The high-resolution N 1s spectrum of CN-meso (Figure C) shows four peaks related to N pyridinic at 398.2 eV (39%), N pyrrolic at 400.6 eV (45%), N graphitic at 402.8 eV (11%), and N oxide at 405 eV (5%). , The major N-species on the carbon frame is N pyrrolic , which is an N species bonded with two carbon in a five-sided ring; they are commonly located on the edges or vacancies of graphitic carbon. Following the Lewis hard–soft interaction principle, N pyrrolic presents an electron-donor nature (Lewis base) and high charge mobility. , N pyrrolic can also act as a link point between the carbon structure and metal species. , …”

Selenium-doped carbon materials: synthesis and applications for sustainable technologies

“…Heteroatom-doped carbonaceous materials constitute attractive metal-free heterogeneous catalysts for a wide range of organic transformations. 132,133 Yu's group designed a new family of Se-doped carbon materials and evaluated them as heterogeneous catalysts in selenium-assisted oxygen transfer processes. 29 The catalyst could be prepared on a kilogram scale by pyrolyzing selenized carbohydrates, such as glucose.…”