The Covalent Functionalization of Layered Black Phosphorus by Nucleophilic Reagents

Sofer, Zdeněk; Bouša, Daniel; Sedmidubský, David; Lazar, Petr; Hartman, Tomáš; Hardtdegen, H.; Pumera, Martin

doi:10.1002/ange.201705722

Cited by 40 publications

(42 citation statements)

References 42 publications

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“…Recently the covalent functionalization of black phosphorus by reaction with various nucleophilic and electrophilic reagents was also reported . The reaction with these type of reagents led dominantly to the formation of P−O−C bonds by reaction with surface oxygen functionalities, but selected strong electrophilic reagents can also form in situ P−C bonds.…”

Section: Modificationsmentioning

confidence: 99%

Chemistry of Layered Pnictogens: Phosphorus, Arsenic, Antimony, and Bismuth

2019

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Materials with few layers have been subjected to extensive research for the last few decades owing to their remarkable properties as for example catalysts, optical and electrical devices, or sensors. The properties and electronic structure of these materials can be tailored by the introduction of substituents. In the case of more reactive species, the modification also can improve stability, which is also an important factor with respect to device fabrication. This review focuses on monoelemental layered materials of Group 15 elements (pnictogens) and in particular their modification, leading to better ambient stability and/or different properties by covalent and non‐covalent modifications. The future modification and application of pnictogens are outlined.

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Section: Modificationsmentioning

confidence: 99%

Chemistry of Layered Pnictogens: Phosphorus, Arsenic, Antimony, and Bismuth

2019

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“…[195,276] Further support may come from theoretical calculations such as DFT, which will help to predict the chemistry, process, and mechanism. [157,189] It is reasonable to expect that, with the continuous effort in the research of chemical functionalization of BPNSs, this area will continue to grow in the coming years and more breakthroughs will emerge to realize their practical applications in various fields.…”

Section: Discussionmentioning

confidence: 99%

“…[67] Fourier-transform infrared spectroscopy (FTIR) measurements can provide information about functional groups present on BPNSs, which show two weak vibrational peaks at 1183 and 1005 cm −1 due to the presence of PO and PO groups from surface oxidation. [157] When BPNSs are further functionalized, the foreign functional groups attached/bounded onto BPNSs can show distinct signals in the FTIR spectrum to help with the structure analysis. 31 P NMR spectroscopy is another possible characterization tool for BPNSs.…”

Section: Characterization Of Bpnssmentioning

confidence: 99%

“…Toward this direction, Pumera and co-workers have demonstrated covalent modifications of BPNSs to form PC and/or POC bonds based on nucleophilic substitution. [157] In their approach, BPNSs were prepared by combination of ultrasonication and shear force milling in organic solvents under argon atmosphere. BPNSs can undergo direct reaction with alkyl halides (Figure 12).…”

Section: Nucleophilic Substitutionmentioning

confidence: 99%

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Recent Advances in Chemical Functionalization of 2D Black Phosphorous Nanosheets

Thurakkal

Zhang

2019

Advanced Science

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BPNSs can be mechanically peeled off from bulk BP crystals using scotch-tape. [37] Although this method can produce high quality 2D BPNSs in a simple and cost-effective manner, the obtained BPNSs show inhomogeneous size, poor repeatability, and extremely low production yield. To obtain BPNSs in a high yield, several alternative methods were employed including metal assisted mechanical exfoliation [102] and exfoliation using polydimethylsiloxane (PDMS) stamp, [70] viscoelastic stamp using blue Nitto tape, [103] and poly(methyl methacrylate)/poly(vinyl alcohol) stack. [104] In another approach, Zhu and co-workers reported a large-scale preparation of relatively stable BPNSs through high energy solid-state mechanical ball milling of bulk BP in the presence of an additive LiOH. [105] The high-energy mechanical milling facilitates the generation of free radicals at the edges by breaking the PP bonds and thus leads to the formation of stable hydroxyl functionalized BPNSs. In addition, this method has been widely utilizing as an efficient method to synthesize functionalized BPNSs for various applications. [106,107] Adv. Sci. 2020, 7, 1902359 3.20-3.73 Å a 1L 2L 3L Bulk Armchair b

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“…Hence, long term stability of BP seems to be the most important issue of BP‐based materials. Several stabilization strategies had been demonstrated, including surface coordination, covalent functionalization, noncovalent functionalization, encapsulation, fluorinated treatment, as well as metal‐ion‐modification . Our group engineered the electronic structure of cobalt nanoparticles/BP nanosheets (Co/BP) catalyst, where by using the active lone‐pairs at the surface of BP, electron migration was realized from BP to Co due to the higher Fermi level of BP than that of Co (Figure a).…”

Section: Bp Based Electrocatalysts For Oermentioning

confidence: 99%

Recent Advances on Black Phosphorus Based Electrocatalysts for Water‐Splitting

Shi

Huang

2020

ChemCatChem

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Hydrogen from electrocatalytic water splitting is a clean and renewable source of sustainable energy. Highly efficient electrocatalyst is of great importance for the low‐cost and large‐scale production of hydrogen. Effective electrocatalysts made of earth abundant elements such as element P have attracted extensive interest. Due to the attractive properties of black phosphorus (BP) including tunable physicochemical characteristics, unique in‐plane anisotropic structure, high charge‐carrier mobility, and large specific surface area, make it stand out from four allotropes. And the breakthrough in BP exfoliation enables it to be a promising 2D platform for designing flexible and versatile BP‐based materials. This review summarizes all these bulk BP, BP nanosheets, BP quantum dots (QDs) as well as BP‐based materials as efficient electrocatalysts in the last several years, with their synthesis methods and electrocatalytic properties for water splitting. Furthermore, some challenges and perspectives for the future development of BP‐based electrocatalysts have been briefly offered.

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The Covalent Functionalization of Layered Black Phosphorus by Nucleophilic Reagents

Cited by 40 publications

References 42 publications

Chemistry of Layered Pnictogens: Phosphorus, Arsenic, Antimony, and Bismuth

Chemistry of Layered Pnictogens: Phosphorus, Arsenic, Antimony, and Bismuth

Recent Advances in Chemical Functionalization of 2D Black Phosphorous Nanosheets

Recent Advances on Black Phosphorus Based Electrocatalysts for Water‐Splitting

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