Selective synthesis of nanosized palladium phosphides from white phosphorus

Kagirov, R. M.; Voloshin, A. V.; Kadirov, Marsil K.; Nizameev, Irek R.; Sinyashin, Оleg G.; Yakhvarov, Dmitry G.

doi:10.1016/j.mencom.2011.07.010

Cited by 12 publications

(8 citation statements)

References 16 publications

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“…The 13 C NMR spectra (Supporting Information, Figure S1) confirm successful fabrication of TiL 4 , with the peak at 20.4 ppm ascribed to carbon in −CH 3 and those at 125.2, 129.3, 139.2, 142.4 ppm stem from carbon atoms in the benzyl group. Transition metals, such as Ag, Au, Cu, Fe, Pd, Cr, and Ti, can be used to prepare metal–phosphorus complexes with other patterns of phosphorus, such as tetrahedral white phosphorus, by coordinating the lone pair electrons of phosphorus in the empty orbital of the metal atoms . Here, the TiL 4 was specifically designed to coordinate with BP because the electrophilic effect of sulfonic ester can strengthen the coordinating ability of titanium…”

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confidence: 90%

Surface Coordination of Black Phosphorus for Robust Air and Water Stability

et al. 2016

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At itanium sulfonate ligand is synthesized for surface coordination of black phosphorus (BP). In contrast to serious degradation observed from the bare BP,the BP after surface coordination exhibits excellent stability during dispersion in water and exposure to air for al ong period of time, therebys ignificantly extending the lifetime and spurring broader application of BP.Atomically thin black phosphorus (BP), an ew member of two-dimensional (2D) materials,h as attracted increasing interest because of its unique electronic and optical properties and promising applications. [1][2][3][4][5][6][7][8][9][10][11][12][13] BP crystals have strong inplane bonds and the weak van der Waals interlayer interaction enables exfoliation into few-layer BP sheets or phosphorene (single-layer BP). [14][15][16][17][18] As am etal-free layered semiconductor,B Ph as thickness-dependent band gaps varying from 0.3 eV for bulk to 2.0 eV for phosphorene. [3] Moreover,B Pw ith high mobility and as izeable band gap is at the electronic intersection of graphene (a zero-gap highmobility 2D material) and semiconducting transition metal dichalcogenides (large-gap low-mobility 2D materials). [2,[19][20][21] These fascinating properties suggest that BP is not only promising in nanoscale electronic devices, [22][23][24][25][26] but also suitable for near-a nd mid-infrared region optoelectronic applications. [27][28][29][30][31] Moreover,BPnanosheets possess excellent photochemical and photothermal properties with potential catalytic and biomedical applications. [11,32] In spite of these promising properties,afundamental obstacle hindering the application of BP is its lack of air-and water-stability. [3] It has been demonstrated that BP is very reactive to oxygen and water under ambient conditions, resulting in compositional and physical changes and consequently considerable degradation in the electronic and optical properties. [10,26,[33][34][35][36] Long-term exposure of BP to humid air or water can even completely etch the materials away.[37] This poses as evere limitation to the adoption of BP in flexible electronics and photoelectronics,a nd its instability in water further limits potential electrochemical and biomedical applications.T herefore,m uch effort has been made to understand the degradation mechanism and to improve the stability of BP. [10,22,[38][39][40][41][42][43] Optical microscopy and atomic force microscopy (AFM) have revealed droplet-like structures on the surface of BP upon exposure to air. [10,37,38] Consequently, capping layers have been developed to encapsulate BP sheets and enhance the air-stability of BP,but oxygen and water may enter through the interfaces causing eventual breakdown. [38] Ther ole of oxygen and water in BP degradation has been studied recently, [42] and it has been shown that degradation of BP under ambient conditions is initiated by contact with oxygen but water does not play aprimary role in the reaction. However,water is capable of removing P x O y from the surface and exposing P 0 to con...

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confidence: 90%

Surface Coordination of Black Phosphorus for Robust Air and Water Stability

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“…The 1 HN MR spectra of TiL 4 in Figure 1d show as ingle peak at 2.2 ppm attributable to hydrogen in the ÀCH 3 group and the two double peaks at 7.2 and 7.5 ppm are associated with hydrogen atoms in the benzyl group.The 13 CNMR spectra (Supporting Information, Figure S1) confirm successful fabrication of TiL 4 ,w ith the peak at 20.4 ppm ascribed to carbon in À CH 3 and those at 125.2, 129.3, 139.2, 142.4 ppm stem from carbon atoms in the benzyl group.T ransition metals,such as Ag, Au, Cu, Fe,P d, Cr,a nd Ti,c an be used to prepare metal-phosphorus complexes with other patterns of phosphorus, such as tetrahedral white phosphorus,b yc oordinating the lone pair electrons of phosphorus in the empty orbital of the metal atoms. [44][45][46][47][48][49] Here,t he TiL 4 was specifically designed to coordinate with BP because the electrophilic effect of sulfonic ester can strengthen the coordinating ability of titanium. [50] In the next step,ultrasmall BP nanosheets (also called BP QDs) were synthesized in N-methyl-2-pyrrolidone (NMP) by al iquid exfoliation technique reported by our group previously, [32] and chosen as one of the BP samples in our coordination study because smaller BP sheets generally undergo faster decomposition.…”

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confidence: 99%

Surface Coordination of Black Phosphorus for Robust Air and Water Stability

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“…We have observed earlier a simi lar signal (singlet at  P -462.3) in the reactions of white phosphorus with palladium(0) complexes which acted as the two electron reducing agents towards P 4 . 18 It follows from the experimental data (see Table 1) that in all above given cases the anode generated metal cations can act as the electrophilic components stabilizing the P 4 2-anions. The process using the aluminum anode is the most efficient.…”

Section: Resultsmentioning

confidence: 93%