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Highly Stable Photocatalytic Dry and Bi-Reforming of Methane with the Role of a Hole Scavenger for Syngas Production over a Defective Co-Doped g-C<sub>3</sub>N<sub>4</sub> Nanotexture
oleh: Muhammad Tahir, Azmat Ali Khan, Abdullah Bafaqeer, Naveen Kumar, Mohammad Siraj, Amanullah Fatehmulla
Format: | Article |
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Diterbitkan: | MDPI AG 2023-07-01 |
Deskripsi
Photocatalytic reduction of CO<sub>2</sub> with CH<sub>4</sub> through the dry reforming of methane (DRM) is an attractive approach to recycling greenhouse gases into valuable chemicals and fuels; however, this process is quite challenging. Although there is growing interest in designing efficient photocatalysts, they are less stable, and have lower photoactivity when employed for DRM reactions. Herein, we developed a noble metal-free hierarchical graphitic carbon nitride (HC<sub>3</sub>N<sub>4</sub>) loaded with cobalt (Co) for highly efficient and stable photocatalytic dry reforming of methane to produce synthesis gases (CO and H<sub>2</sub>). The performance of the newly designed Co/HC<sub>3</sub>N<sub>4</sub> composite was tested for different reforming systems such as the dry reforming of methane, bi-reforming of methane (BRM) and reforming of CO<sub>2</sub> with methanol–water. The performance of HC<sub>3</sub>N<sub>4</sub> was much higher compared to bulk g-C<sub>3</sub>N<sub>4</sub>, whereas Co/HC<sub>3</sub>N<sub>4</sub> was found to be promising for higher charge carrier separation and visible light absorption. The yield of CO and H<sub>2</sub> with HC<sub>3</sub>N<sub>4</sub> was 1.85- and 1.81-fold higher than when using g-C<sub>3</sub>N<sub>4</sub> due to higher charge carrier separation. The optimized 2% Co/HC<sub>3</sub>N<sub>4</sub> produces CO and H<sub>2</sub> at an evolution rate of 555 and 41.2 µmol g<sup>−1</sup> h<sup>−1</sup>, which was 18.28- and 1.74-fold more than using HC<sub>3</sub>N<sub>4</sub> during photocatalytic dry reforming of methane (DRM), with a CH<sub>4</sub>/CO<sub>2</sub> feed ratio of 1.0. This significantly enhanced photocatalytic CO and H<sub>2</sub> evolution during DRM was due to efficient charge carrier separation in the presence of Co. The CH<sub>4</sub>/CO<sub>2</sub> feed ratio was further investigated, and a 2:1 ratio was best for CO production. In contrast, the highest H<sub>2</sub> was produced with a 1:1 feed ratio due to the competitive adsorption of the reactants over the catalyst surface. The performance of the composite was further investigated for bi-reforming methane and methanol. Using photocatalytic CO<sub>2</sub> reduction with CH<sub>4</sub>/H<sub>2</sub>O, the production of CO and H<sub>2</sub> was reduced, whereas significantly higher CO and H<sub>2</sub> evolved using the BRM process involving methanol. Using methanol with CO<sub>2</sub> and H<sub>2</sub>O, 10.77- and 1.39-fold more H<sub>2</sub> and CO efficiency was achieved than when using dry reforming of methane. The composite was also very stable for continuous synthesis gas production during DRM in consecutive cycles. Thus, a co-assisted g-C<sub>3</sub>N<sub>4</sub> nanotexture is promising for promoting photocatalytic activity and can be further explored in other solar energy applications.