Abstract

Vitamin B3 (nicotinic acid, VB3) was synthesized through the photocatalytic oxidation of 3-pyridinemethanol (3PM) under visible-light-emitting diode (LED) irradiation using metal-free graphitic carbon nitride (GCN) - based materials. A bulk (GCN) material was prepared by a simple thermal treatment using dicyandiamide as the precursor. A post-thermal treatment under static air and nitrogen flow was employed to obtain the GCN-T and GCN-T-N materials, respectively. The conditions adopted during the post-treatment revealed differences in the resulting materials’ morphological, electronic, and optical properties. The post-treated photocatalysts revealed an enhanced efficiency in the oxidation of 3PM into VB3, with the GCN-T-N photocatalyst being the best-performing material. The defective surface, reduced crystallinity, and superior photoabsorption of GCN-T-N account for this material’s improved performance in the production of VB3. Nevertheless, the presence of nitrogen vacancies in the carbon nitride structure and, consequently, the creation of mid-gap states also accounts to its highly oxidative ability. The immobilization of GCN-T-N in sodium alginate hydrogel was revealed as a promising strategy to produce VB3, avoiding the need for the photocatalyst separation step. Concerning the mechanism of synthesis of VB3 through the photocatalytic oxidation of 3PM, it was possible to identify the presence of 3-pyridinecarboxaldehyde (3PC) as the intermediary product.

Highlights

  • Vitamin B3 is a water-soluble vitamin that acts as a building block in the synthesis of nicotinamide-adenine-dinucleotide (NAD), playing an essential role in the redox reactions occurring in living cells [1]

  • Bulk graphitic carbon nitride (GCN) and thermally post-treated materials under air (GCN-T) and nitrogen (GCN-T-N) atmosphere were morphologically characterized through scanning electron microscopy (SEM)

  • The photocatalytic performance of GCN, GCN-T, and GCN-T-N materials was studied in the selective oxidation of 3-pyridinemethanol (3PM) into Vitamin B3 (VB3) under visibleLED irradiation

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Summary

Introduction

Vitamin B3 (or nicotinic acid) is a water-soluble vitamin that acts as a building block in the synthesis of nicotinamide-adenine-dinucleotide (NAD), playing an essential role in the redox reactions occurring in living cells [1]. Most vitamin B3 is chemically produced by the ammoxidation and oxidation of pyridines under high pressure and alkali conditions, with a massive energetic demand and the generation of hazardous effluents [1,3]. Heterogeneous photocatalysis has been explored as a valuable and more sustainable alternative to the conventional synthesis processes, using 3-pyridinemethanol as a starting molecule. Spasiano et al [3] used titanium dioxide (TiO2 ) photocatalyst to convert 3-pyridinemethanol into vitamin B3 without oxygen under a high-pressure UV lamp, achieving a 30% conversion and 87% selectivity after 0.75 h of irradiation.

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