Search results for "black phosphorus"

2020 Roadmap on two-dimensional nanomaterials for environmental catalysis

2019

Abstract Environmental catalysis has drawn a great deal of attention due to its clean ways to produce useful chemicals or carry out some chemical processes. Photocatalysis and electrocatalysis play important roles in these fields. They can decompose and remove organic pollutants from the aqueous environment, and prepare some fine chemicals. Moreover, they also can carry out some important reactions, such as O2 reduction reaction (ORR), O2 evolution reaction (OER), H2 evolution reaction (HER), CO2 reduction reaction (CO2RR), and N2 fixation (NRR). For catalytic reactions, it is the key to develop high-performance catalysts to meet the demand for targeted reactions. In recent years, two-dimen…

Cover Feature: Controlling the Formation of Sodium/Black Phosphorus IntercalationCompounds Towards High Sodium Content (8/2021)

2021

Covalent and non-covalent chemistry of 2D black phosphorus

2021

The post-graphene era is undoubtedly marked by two-dimensional (2D) sheet polymers, such as black phosphorus (BP). This emerging material has a fascinating structure and outstanding electronic properties and has been postulated for a plethora of applications. The need to circumvent the pronounced oxophilicity of P atoms has dominated the research on this material in recent years, with the objective of finding the most effective method to improve its environmental stability. When it comes to chemical functionalization, the few approaches reported so far involve some drawbacks such as low degree of addition and low production ability. This review presents the concepts and strategies of our st…

Controlling the Formation of Sodium/Black Phosphorus IntercalationCompounds Towards High Sodium Content

2021

The solid-state synthesis of pure sodium-black phosphorus intercalation compounds (Na-BPICs) has been optimized in bulk for two stoichiometric ratios. Specifically, in-situ X-Ray diffraction (XRD) allowed the precise identification of the optimal temperature range for the formation of Na-BPICs: 94°C–96°C. Moreover, as the undesired formation of Na3P takes place at this very same range, we succeeded in introducing a new synthetic route based on a fast-thermal ball milling implementation that results in the bulk production of BPIC without Na3P in 9 out of 10 cases. Finally, by combining XRD, Raman spectroscopy, and DFT calculations we developed a new structural model for Na-based BPICs showin…

Cover Feature: Few‐layer Black Phosphorous Catalyzes Radical Additions to Alkenes Faster than Low‐valence Metals (ChemCatChem 8/2020)

2020

Quantifying the Covalent Functionalization of Black Phosphorus

2020

Abstract A straightforward quantification method to consistently determine the overall functionalization degree of covalently modified two‐dimensional (2D) black phosphorus (BP) by Raman spectroscopy has been carried out. Indeed, the successful reductive methylation of the BP lattice using sodium intercalation compounds and exhibiting different functionalization degrees has been demonstrated by 31P‐magic angle spinning (MAS) NMR spectroscopy. Furthermore, the correlation of 31P‐MAS NMR spectroscopy and statistical Raman spectroscopy (SRS) revealed the first method to determine the functionalization degree of BP solely by evaluating the intensities of distinct peaks in the Raman spectra of t…

Lattice Opening upon Bulk Reductive Covalent Functionalization of Black Phosphorus

2019

The chemical bulk reductive covalent functionalization of thin-layer black phosphorus (BP) using BP intercalation compounds has been developed. Through effective reductive activation, covalent functionalization of the charged BP by reaction with organic alkyl halides is achieved. Functionalization was extensively demonstrated by means of several spectroscopic techniques and DFT calculations; the products showed higher functionalization degrees than those obtained by neutral routes.

Noncovalent Functionalization and Passivation of Black Phosphorus with Optimized Perylene Diimides for Hybrid Field Effect Transistors

2020

Amongst the different existing methods to passivate black phosphorus (BP) from environmental degradation, the noncovalent functionalization with perylene diimides (PDI) has been postulated as one of the most promising routes because it allows preserving its electronic properties. This work describes the noncovalent functionalization and outstanding environmental protection of BP with tailor made PDI having peri-amide aromatic side chains, which include phenyl and naphthyl groups, exhibiting a significantly increased molecule-BP interaction. These results are rationalized by density functional theory (DFT) calculations showing that the adsorption energies are mainly governed by van der Waals…

Few-layer Black Phosphorous Catalyzes Radical Additions to Alkenes Faster than Low-valence Metals

2020

Abstract The substitution of catalytic metals by p‐block main elements has a tremendous impact not only in the fundamentals but also in the economic and ecological fingerprint of organic reactions. Here we show that few‐layer black phosphorous (FL‐BP), a recently discovered and now readily available 2D material, catalyzes different radical additions to alkenes with an initial turnover frequency (TOF0) up to two orders of magnitude higher than representative state‐of‐the‐art metal complex catalysts at room temperature. The corresponding electron‐rich BP intercalation compound (BPIC) KP6 shows a nearly twice TOF0 increase with respect to FL‐BP. This increase in catalytic activity respect to t…

Interface Amorphization of Two‐Dimensional Black Phosphorus upon Treatment with Diazonium Salts

2021

Abstract Two‐dimensional (2D) black phosphorus (BP) represents one of the most appealing 2D materials due to its electronic, optical, and chemical properties. Many strategies have been pursued to face its environmental instability, covalent functionalization being one of the most promising. However, the extremely low functionalization degrees and the limitations in proving the nature of the covalent functionalization still represent challenges in many of these sheet architectures reported to date. Here we shine light on the structural evolution of 2D‐BP upon the addition of electrophilic diazonium salts. We demonstrated the absence of covalent functionalization in both the neutral and the r…