Black Phosphorus Revisited: A Missing Metal‐Free Elemental Photocatalyst for Visible Light Hydrogen Evolution

Zhu, Xianjun; Zhang, Taiming; Sun, Zijun; Chen, Huan-Lin; Guan, Jian; Chen, Xiang; Ji, Hengxing; Du, Pingwu; Yang, Shangfeng

doi:10.1002/adma.201605776

Cited by 452 publications

(407 citation statements)

References 65 publications

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“…[37][38][39] Among them, graphitic carbon nitride (g-C 3 N 4 ), as the most stable allotrope of carbon nitrides under ambient conditions, has a unique structure comprised of a 2D sheet of tri-s-triazine connected via tertiary amines. [40][41][42][43][44] However, with a relatively large band gap (≈2.7 eV) and the existence of contact resistance between the nanosheets, g-C 3 N 4 exhibits a poor electrical conductivity and low photocatalytic activity owing to the rapid recombination of photogenerated electron-hole pairs. In particular, g-C 3 N 4 , with a moderate band gap and indirect-semiconductor nature, has become a promising metal-free catalyst for water splitting and the degradation of pollutants due to the advantages of low cost and high specific surface area (2500 m 2 g −1 for the monolayer) and has been applied in organic solar cells.…”

Section: Introductionmentioning

confidence: 99%

Hybrids of Fullerenes and 2D Nanomaterials

2018

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Fullerene has a definite 0D closed‐cage molecular structure composed of merely sp2‐hybridized carbon atoms, enabling it to serve as an important building block that is useful for constructing supramolecular assemblies and micro/nanofunctional materials. Conversely, graphene has a 2D layered structure, possessing an exceptionally large specific surface area and high carrier mobility. Likewise, other emerging graphene‐analogous 2D nanomaterials, such as graphitic carbon nitride (g‐C3N4), transition‐metal dichalcogenides (TMDs), hexagonal boron nitride (h‐BN), and black phosphorus (BP), show unique electronic, physical, and chemical properties, which, however, exist only in the form of a monolayer and are typically anisotropic, limiting their applications. Upon hybridization with fullerenes, noncovalently or covalently, the physical/chemical properties of 2D nanomaterials can be tailored and, in most cases, improved, significantly extending their functionalities and applications. Here, an exhaustive review of all types of hybrids of fullerenes and 2D nanomaterials, such as graphene, g‐C3N4, TMDs, h‐BN, and BP, including their preparations, structures, properties, and applications, is presented. Finally, the prospects of fullerene‐2D nanomaterial hybrids, especially the opportunity of creating unknown functional materials by means of hybridization, are envisioned.

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Section: Introductionmentioning

confidence: 99%

Hybrids of Fullerenes and 2D Nanomaterials

2018

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“…[10][11][12][13][14] The layer-dependent direct bandgap ranging between 0.3 and 2.0 eV makes BP a promising absorber of broad solar light extending into the infrared region. [21][22][23][24][25][26] A 2D black phosphorus/platinum heterostructure (Pt/BP) is developed as a highly efficient photocatalyst for solar-driven chemical reactions. [20] These properties of BP are unique from the perspective of solar energy conversion by photocatalysis and have been demonstrated in H 2 evolution and degradation reactions.…”

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confidence: 99%

Black Phosphorus/Platinum Heterostructure: A Highly Efficient Photocatalyst for Solar‐Driven Chemical Reactions

et al. 2018

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A 2D black phosphorus/platinum heterostructure (Pt/BP) is developed as a highly efficient photocatalyst for solar-driven chemical reactions. The heterostructure, synthesized by depositing BP nanosheets with ultrasmall (≈1.1 nm) Pt nanoparticles, shows strong Pt-P interactions and excellent stability. The Pt/BP heterostructure exhibits obvious P-type semiconducting characteristics and efficient absorption of solar energy extending into the infrared region. Furthermore, during light illumination, accelerated charge separation is observed from Pt/BP as manifested by the ultrafast electron migration (0.11 ps) detected by a femtosecond pump-probe microscopic optical system as well as efficient electron accumulation on Pt revealed by in situ X-ray photoelectron spectroscopy. These unique properties result in remarkable performance of Pt/BP in typical hydrogenation and oxidation reactions under simulated solar light illumination, and its efficiency is much higher than that of other common Pt catalysts and even much superior to that of conventional thermal catalysis. The 2D Pt/BP heterostructure has enormous potential in photochemical reactions involving solar light and the results of this study provide insights into the design of next-generation high-efficiency photocatalysts.

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“…The overall results are in agreement with recent X-ray photoemission spectroscopic measurement, which indicates the abundance of P−O bonds over P−O−P bonds. [36] Similarly, sulfur is absorbed at the dangling site, however, the binding energy is much smaller than O absorption. This can be explained as the electronegativity of P and S atoms are comparable, and thus the corresponding P−S bond is nonpolar and longer (1.95 A).…”

Section: Resultsmentioning

confidence: 99%

Photocatalytic Activity of Phosphorene Derivatives: Coverage, Electronic, Optical and Excitonic properties

Arra¹,

Ramya²,

Babar³

et al. 2017

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In the context of two-dimensional metal-free photocatalyst, we investigate the electronic, optical and excitonic properties of phosphorene derivatives within first-principles approach. While two-dimensional phosphorene does not catalyze the complete water splitting reactions, O, S, and N coverages improve the situation drastically, and become susceptible to catalyze the complete reaction at certain coverages. We find that for all these dopants, 0.25 -0.5 ML coverages are thermodynamically more stable, and does not introduce midgap defect states and the composite systems remain semiconducting along with properly aligned valance and conduction bands. Further, within visible light excitation, the optical absorption remain very high 10 5 cm −1 in these composite systems, and the fundamental optical anisotropy of phosphorene remains intact. We also investigate the effect of layer thickness through bilayer phosphorene with oxygen coverages. Finally we investigate the excitonic properties in these composite materials that are conducive to both redox reactions.

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Black Phosphorus Revisited: A Missing Metal‐Free Elemental Photocatalyst for Visible Light Hydrogen Evolution

Cited by 452 publications

References 65 publications

Hybrids of Fullerenes and 2D Nanomaterials

Hybrids of Fullerenes and 2D Nanomaterials

Black Phosphorus/Platinum Heterostructure: A Highly Efficient Photocatalyst for Solar‐Driven Chemical Reactions

Photocatalytic Activity of Phosphorene Derivatives: Coverage, Electronic, Optical and Excitonic properties

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