2D Black Phosphorus–Based Biomedical Applications

Semiconductor photocatalysis, a sustainable and renewable technology, is deemed to be a new path to resolve environmental pollution and energy shortage. The development of effective photocatalysts, especially the metal-free photocatalysts, is a critical determinant of this technique. The recently emerged 2D material of black phosphorus with distinctive properties of tunable direct bandgap, ultrahigh charge mobility, fortified optical absorption, large specific surface area, and anisotropic structure has captured enormous attention since the first exfoliation of bulk black phosphorus into mono- or few layered phosphorene in 2014. In this article, the state-of-the-art preparation methods are first summarized for bulk black phosphorus, phosphorene, and black phosphorus quantum dot and then the fundamental structure and electronic and optical properties are analyzed to evaluate its feasibility as a metal-free photocatalyst. Various modifications on black phosphorus are also summarized to enhance its photocatalytic performance. Furthermore, the multifarious applications such as solar to energy conversion, organic removal, disinfection, nitrogen fixation, and photodynamic therapy are discussed and some of the future challenges and opportunities for black phosphorus research are proposed. This review reveals that the rising star of black phosphorus will be a multifunctional material in the postgraphene era.

Black Phosphorus, a Rising Star 2D Nanomaterial in the Post-Graphene Era: Synthesis, Properties, Modifications, and Photocatalysis Applications

Few-layered exfoliated black phosphorus (EBP) has attracted surging interest for electronics, optoelectronics, and catalysis. As compared to excellent progress in electronic and optoelectronic applications, very few reports are available for electrocatalysis by metal-free EBPs. Herein, we couple solution-processable ultrathin EBP nanosheets with higher Fermi level of N-doped graphene (NG) into a new metal-free 2D/2D heterostructure (EBP@NG) with well-designed interfaces and unique electronic configuration, as efficient and durable bifunctional catalysts toward hydrogen evolution and oxygen evolution reactions (HER/OER) for overall water splitting in alkaline media. By rational interface engineering, the synergy of EBP and NG is fully exploited, which not only improves the stability of EBP, but also effectively modulates electronic structures of each component to boost their intrinsic activities. Specifically, due to the lower Fermi level of EBP relative to NG, their electronic interaction induces directio...

Ultrathin Black Phosphorus-on-Nitrogen Doped Graphene for Efficient Overall Water Splitting: Dual Modulation Roles of Directional Interfacial Charge Transfer.

The use of photothermal agents (PTAs) in cancer photothermal therapy (PTT) has shown promising results in clinical studies. The rapid degradation of PTAs may address safety concerns but usually limits the photothermal stability required for efficacious treatment. Conversely, PTAs with high photothermal stability usually degrade slowly. The solutions that address the balance between the high photothermal stability and rapid degradation of PTAs are rare. Here, we report that the inherent Cu2+-capturing ability of black phosphorus (BP) can accelerate the degradation of BP, while also enhancing photothermal stability. The incorporation of Cu2+ into BP@Cu nanostructures further enables chemodynamic therapy (CDT)-enhanced PTT. Moreover, by employing 64Cu2+, positron emission tomography (PET) imaging can be achieved for in vivo real-time and quantitative tracking. Therefore, our study not only introduces an "ideal" PTA that bypasses the limitations of PTAs, but also provides the proof-of-concept application of BP-based materials in PET-guided, CDT-enhanced combination cancer therapy.

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Marriage of black phosphorus and Cu 2+ as effective photothermal agents for PET-guided combination cancer therapy

Fullerenes possess high chemical stability, large specific surface area, good electrical conductivity and unique three-dimensional structure. In this paper, we provide a general overview of the latest research results of fullerene-based photocatalysts. Firstly, the current status of semiconductor materials and fullerenes in photocatalytic applications are briefly introduced. Secondly, introduced action mechanisms of photocatalysts modified by fullerene C60 and its derivatives, including basic structure, exclusive properties and its effect in photocatalysis and material preparation process. Thirdly, factors affecting material effectiveness and the synthesis strategy of composite photocatalyst modified by fullerene are introduced. Meanwhile, the application advances of the photocatalysts are introduced, including in the degradation of pollutants, organic synthesis, hydrogen production, antibacterial and disinfection in water. Finally, the development trends of fullerenes and their derivatives in photocatalysis are also summarized, including theoretical calculations, the morphological structure control, stable derivatives and increase the selectivity, and new other types of fullerene materials.

Advances in photocatalysis based on fullerene C60 and its derivatives: Properties, mechanism, synthesis, and applications

Few-layer black phosphorus (BP) with an anisotropic two-dimensional (2D)-layered structure shows potential applications in photoelectric conversion and photocatalysis, but is easily oxidized under ambient condition preferentially at its edge sites. Improving the ambient stability of BP nanosheets has been fulfilled by chemical functionalization, however this functionalization is typically non-selective. Here we show that edge-selective functionalization of BP nanosheets by covalently bonding stable C60 molecules leads to its significant stability improvement. Owing to the high stability of the hydrophobic C60 molecule, C60 functions as a sacrificial shield and effectively protects BP nanosheets from oxidation under ambient condition. C60 bonding leads to a rapid photoinduced electron transfer from BP to C60, affording enhanced photoelectrochemical and photocatalytic activities. The selective passivation of the reactive edge sites of BP nanosheets by sacrificial C60 molecules paves the way toward ambient processing and applications of BP.

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Stabilizing black phosphorus nanosheets via edge-selective bonding of sacrificial C 60 molecules.

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.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/advs.201800941

Hybrids of Fullerenes and 2D Nanomaterials.

According to the isolated pentagon rule (IPR), for stable fullerenes, the 12 pentagons should be isolated from one another by hexagons, otherwise the fused pentagons will result in an increase in the local steric strain of the fullerene cage. However, the successful isolation of more than 100 endohedral and exohedral fullerenes containing fused pentagons over the past 20 years has shown that strain release of fused pentagons in fullerene cages is feasible. Herein, we present a general overview on fused-pentagon-containing (i.e. non-IPR) fullerenes through an exhaustive review of all the types of fused-pentagon-containing fullerenes reported to date. We clarify how the strain of fused pentagons can be released in different manners, and provide an in-depth understanding of the role of fused pentagons in the stability, electronic properties, and chemical reactivity of fullerene cages.

Strain Release of Fused Pentagons in Fullerene Cages by Chemical Functionalization.

Hybridizing MoS2 and C60 via a van der Waals heterostructure toward synergistically enhanced visible light photocatalytic hydrogen production activity

Despite recent successes in preparing three-dimensional crystals of empty fullerenes, such as C60 and C70 , 3D endohedral fullerene crystals, and especially hollow nanostructures, have been scarcely reported. A universal approach has now been developed to prepare shape-tunable 3D crystals of several metal nitride clusterfullerenes, including cubes and dice (hollow cubes with holes at the center of each face), which can be readily switched by changing the volume ratio of good (mesitylene) and poor (isopropanol) solvents. Synchrotron-based soft X-ray nano-computed tomography was used to unambiguously identify the interior microstructure of the dice-shaped crystals of Tb3 N@C80 , and especially the depth of the hole at each face, confirming that the dice has a solid center and the holes are not interconnected. Owing to the enhanced light absorption, the dice-shaped crystals exhibit enhanced photoluminescence relative to that of the cubes.

Runnan Guan

Papers

Stabilizing black phosphorus nanosheets via edge-selective bonding of sacrificial C 60 molecules.

Hybrids of Fullerenes and 2D Nanomaterials.

Strain Release of Fused Pentagons in Fullerene Cages by Chemical Functionalization.

Hybridizing MoS2 and C60 via a van der Waals heterostructure toward synergistically enhanced visible light photocatalytic hydrogen production activity

From Cubes to Dice: Solvent-Regulated Morphology Engineering of Endohedral Fullerene Microcrystals with Anomalous Photoluminescence Enhancement