Elsevier

Surfaces and Interfaces

Volume 26, October 2021, 101394
Surfaces and Interfaces

Visible light active Boron doped phenyl-g-C3N4 nanocomposites for decomposition of Dyes

https://doi.org/10.1016/j.surfin.2021.101394Get rights and content

Abstract

The use of graphitic-C3N4 as a photocatalyst has gathered enormous attention in the area of photocatalysis. Herein, Boron doped phenyl ring incorporated (PhCN) is set up by the hydrothermal technique using various synthons like benzamide, urea, and boron oxide. The prepared active catalyst is characterized by using standard analytical techniques. The activity of the synthesized xB/PhCN is tested by studying the decolorization of methyl orange (MO) and rhodamine B (RhB) under illumination. All synthesized composites (B-doped-PhCN) showed better activity compared with a pure sample of PhCN. The XRD patterns indicate that the most active catalyst is quite a stable catalyst even after the photolysis experiment. The mechanistic pathway studied via trapping of main reactive species indicates that hydroxide radical (OH), and superoxide radical anions (O2•−) play a major role in the photooxidation of both dyes. In light of this, a reasonable route for photooxidation of pollutants via charge carrier separation has been proposed.

Introduction

In the past few years, semiconducting materials have been widely utilized for the degradation of harmful organics [1], [2], [3], [4], [5]. Also, various sort of obvious light-susceptible photocatalysts, including Titanium dioxide-modified and other semiconductor materials, have been studied [6], [7], [8], [9], [10].

Among these semiconductor materials, the g-C3N4 is recognized as an active metal-free semiconductor due to its favorable physical and chemical properties [11], [12], [13]. A simple process can be used for its preparation from any one of the commercially available materials such as thiourea, urea, melamine, or dicyandiamide via thermal polymerization techniques. This material showed a good performance for water detoxification and bacteria disinfection [14], [15] but with low activity in visible light [16], [17]. Therefore, various methods have been developed to improve the efficacy and absorptivity of solar light for the excitation of g-nitride. The various methods used for its modification involve metal/non-metal doping [18], [19], [20], [21], [22], [23], or the development of composite with suitable semiconductors [24]. Also, porous nanostructure design [25], two-dimensional nanosheets [26], [27], [28], [29], and the construction of heterojunction have also been employed as well [30], [31], [32], [33]. The elemental doping was considered as an efficacious strategy to adjust the photocatalyst's electronic structure for its absorption at a higher wavelength. [34]. Furthermore, the thin 2D-nanosheet-like structure showed better activity because of an increase in surface area and enhancement in the lifetime of excitons [27]. The activity of g-C3N4 with dopants like O, H, N, and S for the removal of organic contaminants has been reported earlier [35].

Besides these studies, the researches on B-doped with g-C3N4 has achieved much attention [36], [37]. Boron-doping can reduce the bandgap, and alter the conductivity from n-type to p-type for g-C3N4 thereby conserving the conduction band edge sufficiently negative for the production of hydrogen [36,[38], [39]]. Recently, co-polymerization is used as a new strategy to produce functionalized g-C3N4 [40] as a stable and effective method. More recently, phenyl incorporated with g-C3N4 was found to display improvement in photocatalysis due to the annulated benzene ring obtained from polymerization of urea and benzamide [41,42]. We explore here for the first time the foundation of composite between boron and phenyl modified-g-C3N4 (xB/PhCN) nanocomposites with different wt % of Boron (0.05, 0.1, 0.2, and 0.3 g) via one-pot calcination of urea, benzamide, and Boron oxide. The catalysts were examined using techniques like XRD, SEM-EDX, TEM, DRS, FTIR, EIS and EPR. The activity of the catalysts was accessed by studying the photooxidation of two different chromophoric dyes [Methyl Orange and Rhodamine B in aqueous suspension under visible simulated light in the presence of atmospheric oxygen].

Section snippets

Experimental section

The experimental details comprising of materials used, catalyst characterization, photocatalytic activity test, and determination of active species involved in the photooxidation of dyes in the presence of a catalyst, visible light, and atmospheric oxygen in the aqueous medium is given in the supplementary file.

XRD analysis

The crystalline structure of synthesized catalysts was evaluated by X-ray diffraction (XRD). The XRD spectra for both PhCN and xB/PhCN samples showed two pronounced absorptions appearing at 12.8° and 27.5° (Fig. 1). The XRD of both samples were found to have no conspicuous contrast between PhCN and xB/PhCN and have a similar crystal structure. The strong peak at 27.5° was the characteristic of an interlayer stacking in an aromatic structure, which was listed to the (002) peak corresponding to

Conclusions

In this work, we design a new approach to prepare B-doped-PhCN incorporating a simple hydrothermal method. All xB/PhCN samples lead to a redshift in the lambda max and a decrease in the bandgap. Among different synthesized samples, 0.2 B/PhCN exhibited a remarkable activity compared with all examined materials for removal of MO and RhB under visible-light illumination. The high performance of the synthesized material could basically be due to extended electron-hole pair charge transport. The

Author agreement statement

We the undersigned declare that this manuscript is original, has not been published before, and is not currently being considered for publication elsewhere.

We confirm that the manuscript has been read and approved by all named authors and that there are no other persons who satisfied the criteria for authorship but are not listed. We further confirm that the order of authors listed in the manuscript has been approved by all of us.

We understand that the Corresponding Author is the sole contact

Declaration of Competing Interest

We don't have any conflicts of interest that may affect our work.

Acknowledgments

The authors acknowledge SERB, the Government of India (CRG/2019/001370), and the Department of Chemistry, AMU, Aligarh, for the financial support to carry out this work. Murad Z. A. Warshagha is thankful to the Indian council for cultural relations (ICCR), for the financial support of his Ph.D. Program.

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