Enhanced photocatalytic hydrogen evolution by partially replaced corner-site C atom with P in g-C3N4

Wang, Bin; Cai, Hairui; Zhao, Daming; Song, Miao; Guo, Peijun; Shen, Shaohua; Li, Dongsheng; Yang, Shengchun

doi:10.1016/j.apcatb.2018.10.044

Cited by 118 publications

(44 citation statements)

References 53 publications

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“…TheP2p spectra displayed 2p 3/2 and 2p 1/2 spin-orbit doublets locating at about 130.1 and 131.0 eV (Figure 2c), which can be attributed to elemental P 0 , [11] while the peak at 133.4 eV was ascribed to P-N coordination, indicating that the Pa toms probably replaced Catoms in the melon units of PCN and created P À Nbonds. [17] Besides,the relative intensity of elemental P 0 in the PCN@HP composites increased depending on the increasing RP amounts added for the CVD procedure.I ti sw orth noting that the peaks of P2pand N1sfor PCN@HP shifted towards the lower binding energy,ascompared to that of HP and PCN. These shifts suggested that the electron transfer from PCN to HP happened in the PCN@HP composites.…”

Section: Resultsmentioning

confidence: 99%

A [001]‐Oriented Hittorf's Phosphorus Nanorods/Polymeric Carbon Nitride Heterostructure for Boosting Wide‐Spectrum‐Responsive Photocatalytic Hydrogen Evolution from Pure Water

Zhu

Yin

et al. 2019

Angewandte Chemie

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Red phosphorus is a promising photocatalyst with wide visible‐light absorption up to 700 nm, but the fast charge recombination limits its photocatalytic hydrogen evolution reaction (HER) activity. Now, [001]‐oriented Hittorf's phosphorus (HP) nanorods were successfully grown on polymeric carbon nitride (PCN) by a chemical vapor deposition strategy. Compared with the bare PCN and HP, the optimized PCN@HP hybrid exhibited a significantly enhanced photocatalytic activity, with HER rates reaching 33.2 and 17.5 μmol h−1 from pure water under simulated solar light and visible light irradiation, respectively. It was theoretically and experimentally indicated that the strong electronic coupling between PCN and [001]‐oriented HP nanorods gave rise to the enhanced visible light absorption and the greatly accelerated photoinduced electron–hole separation and transfer, which benefited the photocatalytic HER performance.

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Section: Resultsmentioning

confidence: 99%

A [001]‐Oriented Hittorf's Phosphorus Nanorods/Polymeric Carbon Nitride Heterostructure for Boosting Wide‐Spectrum‐Responsive Photocatalytic Hydrogen Evolution from Pure Water

Zhu

Yin

et al. 2019

Angewandte Chemie

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“…Since the pioneering work reported in 2009 by Wang et al, metal‐free graphitic carbon nitride (g‐C 3 N 4 ) with a 2D conjugated structure has been intensively investigated for photocatalytic water redox reactions, owing to its earth‐abundance, environmental friendliness, chemical stability, and suitable thermodynamical potentials for both hydrogen and oxygen evolution reactions . In the past ten years, various strategies, including thermodynamic (such as doping with heteroatoms, engineering defects with nitrogen vacancies or carbon vacancies, etc.) and kinetic (such as compositing with other semiconductors, morphology design, and loading cocatalysts, etc.)…”

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“…Recently, dopants or defects were introduced into the 2D g‐C 3 N 4 framework to significantly enhance the photocatalytic activity by engineering the band structure and the electronic structure for the improved optical absorption ability and the promoted charge carrier transfer kinetics . For instance, Cheng and co‐workers successfully doped sulfur into g‐C 3 N 4 via calcining g‐C 3 N 4 powder in hydrogen sulfide atmosphere, with photocatalytic activity for hydrogen evolution greatly improved by 7.2 times as compared to pristine g‐C 3 N 4 , due to the elevated conduction band (CB) giving rise to the increased driving force water reduction .…”

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Synergy of Dopants and Defects in Graphitic Carbon Nitride with Exceptionally Modulated Band Structures for Efficient Photocatalytic Oxygen Evolution

et al. 2019

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As inspired by natural photosynthesis, semiconductor-based photocatalytic water splitting into hydrogen and oxygen has attracted extensive attention, which provides a promising and clean method to convert solar energy into chemical fuel, for alleviating human's excessive reliance on fossil fuels. [1][2][3] For the water splitting process, the half-reaction of water oxidation to oxygen has been well recognized as the rate-limiting step for its four-electron oxidation process and high activation energy barrier (≈700 mV) for O-O bond formation, [4,5] which thus remains as the main challenge to achieve highly efficient overall water splitting. Although enormous efforts have been dedicated to develop photocatalysts for improved water oxidation performances in the past decades, by far only a few photocatalysts (e.g., WO 3 , BiVO 4 , and Ag 3 PO 4 , etc.) have been proven to be efficient for lightdriven oxygen evolution from water. [5][6][7][8] Worse still, several drawbacks always limit their practical application in oxygen-generating photocatalytic systems, including poor photostability, low charge carrier mobility, and high costs of raw materials. Since the pioneering work reported in 2009 by Wang et al., [9] metal-free graphitic carbon nitride (g-C 3 N 4 ) with a 2D conjugated structure has been intensively investigated for photocatalytic water redox reactions, owing to its earth-abundance, environmental friendliness, chemical stability, and suitable thermodynamical potentials for both hydrogen and oxygen evolution reactions. [10][11][12] In the past ten years, various strategies, including thermodynamic (such as doping with heteroatoms, [13][14][15][16] engineering defects with nitrogen vacancies or carbon vacancies, [17,18] etc.) and kinetic (such as compositing with other semiconductors, [7,[19][20][21][22] morphology design, [23][24][25][26][27] and loading cocatalysts, [28][29][30] etc.) modifications, have emerged to enhance the photocatalytic hydrogen evolution activity of g-C 3 N 4 and a high quantum yield of 34.4% at 400 nm has been achieved. [31] However, only very few results have been reported on g-C 3 N 4 based photocatalysts for water oxidation, and most of them were focused on surface modification by loading cocatalysts, such as cobalt (hydr)oxide and selenide, [32][33][34] etc., onto g-C 3 N 4 . Unfortunately, the photocatalytic oxygen evolution Electronic structure greatly determines the band structures and the charge carrier transport properties of semiconducting photocatalysts and consequently their photocatalytic activities. Here, by simply calcining the mixture of graphitic carbon nitride (g-C 3 N 4 ) and sodium borohydride in an inert atmosphere, boron dopants and nitrogen defects are simultaneously introduced into g-C 3 N 4 . The resultant boron-doped and nitrogen-deficient g-C 3 N 4 exhibits excellent activity for photocatalytic oxygen evolution, with highest oxygen evolution rate reaching 561.2 µmol h −1 g −1 , much higher than previously reported g-C 3 N 4 . It is well evidenced that with c...

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“…The light absorption properties of samples were studied by UV–visible spectroscopy (Figure S13a, Supporting Information). Pure g‐C 3 N 4 shows a clear absorption band edge at 460 nm, indicating a bandgap of 2.7 eV . After B‐doping, obvious tailing peaks can be observed in the range of 450–550 nm.…”

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Graphitic Carbon Nitride with Dopant Induced Charge Localization for Enhanced Photoreduction of CO₂ to CH₄

et al. 2019

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The photoreduction of CO2 to hydrocarbon products has attracted much attention because it provides an avenue to directly synthesize value‐added carbon‐based fuels and feedstocks using solar energy. Among various photocatalysts, graphitic carbon nitride (g‐C3N4) has emerged as an attractive metal‐free visible‐light photocatalyst due to its advantages of earth‐abundance, nontoxicity, and stability. Unfortunately, its photocatalytic efficiency is seriously limited by charge carriers′ ready recombination and their low reaction dynamics. Modifying the local electronic structure of g‐C3N4 is predicted to be an efficient way to improve the charge transfer and reaction efficiency. Here, boron (B) is doped into the large cavity between adjacent tri‐s‐triazine units via coordination with two‐coordinated N atoms. Theoretical calculations prove that the new electron excitation from N (2px, 2py) to B (2px, 2py) with the same orbital direction in B‐doped g‐C3N4 is much easier than N (2px, 2py) to C 2pz in pure g‐C3N4, and improves the charge transfer and localization, and thus the reaction dynamics. Moreover, B atoms doping changes the adsorption of CO (intermediate), and can act as active sites for CH4 production. As a result, the optimal sample of 1%B/g‐C3N4 exhibits better selectivity for CH4 with ≈32 times higher yield than that of pure g‐C3N4.

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Enhanced photocatalytic hydrogen evolution by partially replaced corner-site C atom with P in g-C3N4

Cited by 118 publications

References 53 publications

A [001]‐Oriented Hittorf's Phosphorus Nanorods/Polymeric Carbon Nitride Heterostructure for Boosting Wide‐Spectrum‐Responsive Photocatalytic Hydrogen Evolution from Pure Water

A [001]‐Oriented Hittorf's Phosphorus Nanorods/Polymeric Carbon Nitride Heterostructure for Boosting Wide‐Spectrum‐Responsive Photocatalytic Hydrogen Evolution from Pure Water

Synergy of Dopants and Defects in Graphitic Carbon Nitride with Exceptionally Modulated Band Structures for Efficient Photocatalytic Oxygen Evolution

Graphitic Carbon Nitride with Dopant Induced Charge Localization for Enhanced Photoreduction of CO₂ to CH₄

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Enhanced photocatalytic hydrogen evolution by partially replaced corner-site C atom with P in g-C3N4

Cited by 118 publications

References 53 publications

A [001]‐Oriented Hittorf's Phosphorus Nanorods/Polymeric Carbon Nitride Heterostructure for Boosting Wide‐Spectrum‐Responsive Photocatalytic Hydrogen Evolution from Pure Water

A [001]‐Oriented Hittorf's Phosphorus Nanorods/Polymeric Carbon Nitride Heterostructure for Boosting Wide‐Spectrum‐Responsive Photocatalytic Hydrogen Evolution from Pure Water

Synergy of Dopants and Defects in Graphitic Carbon Nitride with Exceptionally Modulated Band Structures for Efficient Photocatalytic Oxygen Evolution

Graphitic Carbon Nitride with Dopant Induced Charge Localization for Enhanced Photoreduction of CO2 to CH4

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Graphitic Carbon Nitride with Dopant Induced Charge Localization for Enhanced Photoreduction of CO₂ to CH₄