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1.
ACS Appl Mater Interfaces ; 14(32): 37076-37087, 2022 Aug 17.
Article in English | MEDLINE | ID: mdl-35925836

ABSTRACT

Photocatalytic N2 fixation has emerged as one of the most useful ways to produce NH3, a useful asset for chemical industries and a carbon-free energy source. Recently, significant progress has been made toward designing efficient photocatalysts to achieve this objective. Here, we introduce a highly active type-II heterojunction fabricated via integrating two-dimensional (2D) nanosheets of exfoliated g-C3N5 with nickel-chromium layered double hydroxide (NiCr-LDH). With an optimized loading of NiCr-LDH on exfoliated g-C3N5, excellent performance is realized for green ammonia synthesis under ambient conditions without any noble metal cocatalyst(s). Indeed, the g-C3N5/NiCr-LDH heterostructure with 2 wt % of NiCr-LDH (CN-NCL-2) exhibits an ammonia yield of about 2.523 mmol/g/h, which is about 7.51 and 2.86 times higher than that of solo catalysts, i.e., NiCr-LDH (NC-L) and exfoliated g-C3N5 (CN-5), respectively, where methanol is used as a sacrificial agent. The enhancement of NH3 evolution by the g-C3N5/NiCr-LDH heterostructure can be attributed to the efficient charge transfer, a key factor to the photocatalytic N2 fixation rate enhancement. Additionally, N2 vacancies present in the system help adsorb N2 on the surface, which improves the ammonia production rate further. The best-performing heterostructure also shows long-term stability with the NH3 production rate remaining nearly constant over 20 h, demonstrating the excellent robustness of the photocatalyst.

2.
Langmuir ; 38(10): 3139-3148, 2022 Mar 15.
Article in English | MEDLINE | ID: mdl-35234471

ABSTRACT

Establishment of an efficient and robust artificial photocatalytic system to convert solar energy into chemical fuels through CO2 conversion is a cherished goal in the fields of clean energy and environmental protection. In this work, we have explored an emergent low-Z nitrogen-rich carbon nitride material g-C3N5 (analogue of g-C3N4) for CO2 conversion under visible light illumination. A significant enhancement of the CH4 production rate was detected for g-C3N5 in comparison to that of g-C3N4. Notably, g-C3N5 also showed a very impressive selectivity of 100% toward CH4 as compared to 21% for g-C3N4. The photocatalytic CO2 conversion was performed without using sacrificial reagents. We found that 1% K doping in g-C3N5 enhanced its performance even further without compromising the selectivity. Moreover, 1% K-doped g-C3N5 also exhibited better photostability than undoped g-C3N5. We have also employed density functional theory calculation-based analyses to understand and elucidate the possible reasons for the better photocatalytic performance of K-doped g-C3N5.

3.
ChemSusChem ; 13(1): 196-204, 2020 Jan 09.
Article in English | MEDLINE | ID: mdl-31549796

ABSTRACT

A 3 D intermetallic anti-perovskite carbide, Fe3 SnC, is reported as a Li-ion battery anode. Single-phase Fe3 SnC showed a reversible Li-ion capacity of 426 mAh g-1 that increased significantly (600 mAh g-1 ) upon its in situ synthesis by electrospinning and pyrolysis to render a conducting carbon nanofibre (CNF) based composite. Importantly, the Fe3 SnC@CNF composite showed excellent stability in up to 1000 cycles with a remarkable 96 % retention of capacity. The rate performance was equally impressive with a high capacity of 500 mAh g-1 delivered at a high current density of 2 A g-1 . An estimation of Li ion diffusion from the electrochemical impedance data showed a major enhancement of the rate by a factor of 2 in the case of Fe3 SnC@CNF compared to the single-phase Fe3 SnC sample. Post-cyclic characterisation revealed that the unit cell was retained despite a volume expansion upon the inclusion of four Li atoms per unit cell, as calculated from the capacity value. The cyclic voltammogram shows four distinctive peaks that could be identified as the sequential incorporation of up to four Li atoms. First-principles DFT calculations were performed to elucidate the favourable sites for the inclusion of 1-4 Li atoms inside the Fe3 SnC unit cell along with the associated strain.

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