Monodispersed nickel phosphide nanocrystals with different phases: synthesis, characterization and electrocatalytic properties for hydrogen evolution

Pan, Yuan; Liu, Yanru; Zhao, Juan; Kang, Yang; Liang, Jiaen; Liu, Dandan; Hu, Wenhui; Liu, Dapeng; Liu, Yunqi; Liu, Chenguang

doi:10.1039/c4ta04867a

Cited by 566 publications

(403 citation statements)

References 62 publications

(31 reference statements)

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“…further confirming that the introduction of nitrogen atom into RGO can facilitate reaction kinetics of HER. In addition, the Tafel slope for Ni 2 P/NRGO also suggests that the HER process occurs a VolmereHeyrovsky mechanism and the Heyrovsky step is the ratedetermining step [42].…”

Section: Resultsmentioning

confidence: 97%

Nickel phosphide nanoparticles-nitrogen-doped graphene hybrid as an efficient catalyst for enhanced hydrogen evolution activity

Pan

Chen

et al. 2015

Journal of Power Sources

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Section: Resultsmentioning

confidence: 97%

Nickel phosphide nanoparticles-nitrogen-doped graphene hybrid as an efficient catalyst for enhanced hydrogen evolution activity

Pan

Chen

et al. 2015

Journal of Power Sources

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155

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“…[ 31,33 ] However, experimental work indicates that phosphides with higher contents of phosphorus would outperform that of lower content. This is manifested in the comparative study of Co 2 P and CoP where on low-index surfaces, more P atoms are exposed in CoP than that of Co 2 P. [ 32 ] Another study of phase-dependent catalytic activity of nickel phosphides, including Ni 12 P 5 , Ni 2 P and Ni 5 P 4 by Pan et al, [ 34 ] also highlights phosphorus and suggests that phosphide with higher P content exhibits higher performance, following the trend Ni 12 P 5 (29%) < Ni 2 P (33%) < Ni 5 P 4 (44%) (Figure 3 e). When the particle size of Ni 2 P and Ni 5 P 4 (shown in Figure 3 c,d) is taken into account, the advantage of the P-rich nature would be more distinct.…”

Section: Organic Phosphinementioning

confidence: 98%

A Review of Phosphide‐Based Materials for Electrocatalytic Hydrogen Evolution

Xiao

Chen

Wang

2015

Advanced Energy Materials

762

425

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for HER when nanoscale MoS 2 is used, [ 1 ] albeit bulk MoS 2 is suggested to be inactive towards HER. [ 2 ] Thus most studies have focused on designing thin layered/nanostructured MoS 2 nanomaterials with most exposed edges for HER. To this end, amorphous MoS 2,[ 3 ] MoS x nanosheets [ 4 ] were found to outperform bulk MoS 2 signifi cantly; layer-dependent attributes, [ 5 ] the correlation with intrinsic low conductivity out-of-plane, and phasedetermined performance have also been studied. [ 6 ] These fi ndings have stimulated the work of sulfi de of earth-abundant metals, e.g., WS 2 [ 7 ] and its analogues, selenides, [ 8 ] resulting in a big family of chalcogenides of fi rst-row transition metals. [ 9 ] Reviews [ 6b , 7c , 10 ] have been conducted from different perspectives and can be referred to accordingly. Unfortunately, the best performing MoS 2 catalyst still lacks the competitiveness of Pt. Furthermore, improvements in performance relies heavily on the basis that moly bdenum/tungsten chalcogenides (sulfi de, selenide) are nanostructured with abundant S-edges and are thin layered (preferable single layer). These requirements may severely constrain their application in large-scale production. Thus, it is imperative to continue the search for new inexpensive catalysts that can rival the performance of Pt while being suitable for large-scale hydrogen production.It was only recently discovered that hydrogen evolution proceeds via a similar pathway to that of hydrogenation (hydrotreating process), e.g., hydrodesulfurization (HDS), where a reversible ad/desorption of hydrogen on catalyst is critical for achieving fast kinetics. This correlation broadens the scope of search for new catalysts. Hence, phosphides, previously employed as catalysts for HDS, were found to be active towards HER, e.g., Ni 2 P [ 11 ] has been reported to achieve a better performance than the state-of-the-art MoS 2 .[ 11c ] This pivotal work [ 11c ] was followed by a variety of studies applying phosphide as catalysts for HER. This class of electrocatalyst with superb electrocatalytic activities has thus opened up a new avenue in the search of non-noble metal catalysts for HER. Here, we focus our discussion on the recent developments of synthesis methodology of phosphides for HER. Based on different synthetic routes of phosphides, we then make a comparative survey of their activities, which are evaluated in terms of experimental metrics of over-potential ( η ) at a certain current density ( j ), Tafel slope coupled with exchange current density ( j o ) extrapolated from the plot of η vs. Log 10 ( j ), and turnover frequency (TOF). In conjunction with experimental results, Hydrogen evolution by means of electrocatalytic water-splitting is pivotal for effi cient and economical production of hydrogen, which relies on the development of inexpensive, highly active catalysts. In addition to sulfi des, the search for non-noble metal catalysts has been mainly directed at phosphides due to the superb activity of phosphides for hydrogen ev...

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“…82 These methods yield nickel phosphide nanocrystals with various morphologies. 83 Their exact phase and composition obtained is affected by the Ni to P ratio, 84,85 counteranions, 86 voltage (in case of electrosynthesis), 87 the identity and concentration of surfactants, 88 the reaction solvent(s), 89 time, and temperature. 90 Some methods call for fine-tuning and optimization of multiple factors in order to achieve satisfactory levels of phase and composition control.…”

Section: ■ Introductionmentioning

confidence: 99%

Phase-Programmed Nanofabrication: Effect of Organophosphite Precursor Reactivity on the Evolution of Nickel and Nickel Phosphide Nanocrystals

et al. 2015

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A better understanding of the chemistry of molecular precursors is useful in achieving more predictable and reproducible nanocrystal preparations. Recently, an efficient approach was introduced that consists of finetuning the chemical reactivity of the synthetic molecular precursors used, while keeping all other reaction conditions constant. Using nickel phosphides as a research platform, we have studied how the chemical structure and reactivity of a family of commercially available organophosphite precursors (P(OR)3, R = alkyl or aryl) alter the preparation of metallic and metal phosphide nanocrystals. Organophosphites are a versatile addition to the pnictide synthetic toolbox, nicely complementing other available precursors such as elemental phosphorus or trioctylphosphine (TOP). Experimental and computational data show that different organophosphite precursors selectively yield Ni, Ni12P5, and Ni2P and that these phases evolve over time through separate mechanistic pathways. Based on our observations, we propose that nickel phosphide formation requires organophosphite coordination to a nickel precursor, followed by intramolecular rearrangement. We also propose that metallic nickel formation involves outer sphere reduction by uncoordinated organophosphite. These two independent pathways are supported by the fact that preformed Ni nanocrystals do not react with some of the most reactive phosphide-forming organophosphites, failing to evolve into nickel phosphide nanocrystals. Overall, the rate at which organophosphites react with nickel(II) chloride or acetate to form nickel phosphides increases in the order P(OMe)3 < P(OEt)3 < P(OnBu)3 < P(OCH2tBu)3 < P(OiPr)3 < P(OPh)3. Some organophosphites, such as P(OMe)3 or P(OiPr)3, transiently form zerovalent, metallic nickel, while this is the only persistent product observed with the bulky organophosphite P(O-2,4-tBu2C6H4)3. We expect that these results will alleviate the need for timeconsuming testing and random optimization of several different reaction conditions, thus enabling a faster development of these and similar pnictide nanomaterials for practical applications. Disciplines Chemistry CommentsReprinted (adapted) with permission from Chemistry of Materials 27 (2015) ABSTRACT: A better understanding of the chemistry of molecular precursors is useful in achieving more predictable and reproducible nanocrystal preparations. Recently, an efficient approach was introduced that consists of fine-tuning the chemical reactivity of the synthetic molecular precursors used, while keeping all other reaction conditions constant. Using nickel phosphides as a research platform, we have studied how the chemical structure and reactivity of a family of commercially available organophosphite precursors (P(OR) 3 , R = alkyl or aryl) alter the preparation of metallic and metal phosphide nanocrystals. Organophosphites are a versatile addition to the pnictide synthetic toolbox, nicely complementing other available precursors such as elemental phosphorus or trioctylphosphine (TO...

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Monodispersed nickel phosphide nanocrystals with different phases: synthesis, characterization and electrocatalytic properties for hydrogen evolution

Abstract: Monodispersed nickel phosphide nanocrystals (NCs) with different phases were successfully synthesized. The Ni5P4 NCs, with a solid structure, exhibited higher catalytic activity than the Ni12P5 and Ni2P NCs.

Cited by 566 publications

References 62 publications

Nickel phosphide nanoparticles-nitrogen-doped graphene hybrid as an efficient catalyst for enhanced hydrogen evolution activity

Nickel phosphide nanoparticles-nitrogen-doped graphene hybrid as an efficient catalyst for enhanced hydrogen evolution activity

A Review of Phosphide‐Based Materials for Electrocatalytic Hydrogen Evolution

Phase-Programmed Nanofabrication: Effect of Organophosphite Precursor Reactivity on the Evolution of Nickel and Nickel Phosphide Nanocrystals

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