Control of Phase in Phosphide Nanoparticles Produced by Metal Nanoparticle Transformation: Fe<sub>2</sub>P and FeP

Muthuswamy, Elayaraja; Kharel, Parashu; Lawes, G.; Brock, Stephanie L.

doi:10.1021/nn900574r

Cited by 103 publications

(114 citation statements)

References 28 publications

(77 reference statements)

Supporting

Mentioning

105

Contrasting

Order By: Relevance

“…24 Transmission electron microscopy (TEM) images ( Figure 1) indicated the formation of spherical, hollow particles with an average diameter of 13 ( 2 nm. The corresponding high-resolution TEM (HRTEM) image ( Figure 1b) revealed that the hollow particles were single crystalline and faceted and are therefore morphologically similar to other transitionmetal phosphide nanoparticles formed by chemically transforming metal seed particles into phosphides using TOP.…”

Section: Resultsmentioning

confidence: 99%

Electrocatalytic and Photocatalytic Hydrogen Production from Acidic and Neutral-pH Aqueous Solutions Using Iron Phosphide Nanoparticles

et al. 2014

View full text Add to dashboard Cite

Nanostructured transition-metal phosphides have recently emerged as Earth-abundant alternatives to platinum for catalyzing the hydrogen-evolution reaction (HER), which is central to several clean energy technologies because it produces molecular hydrogen through the electrochemical reduction of water. Iron-based catalysts are very attractive targets because iron is the most abundant and least expensive transition metal. We report herein that iron phosphide (FeP), synthesized as nanoparticles having a uniform, hollow morphology, exhibits among the highest HER activities reported to date in both acidic and neutral-pH aqueous solutions. As an electrocatalyst operating at a current density of -10 mA cm(-2), FeP nanoparticles deposited at a mass loading of ∼1 mg cm(-2) on Ti substrates exhibited overpotentials of -50 mV in 0.50 M H2SO4 and -102 mV in 1.0 M phosphate buffered saline. The FeP nanoparticles supported sustained hydrogen production with essentially quantitative faradaic yields for extended time periods under galvanostatic control. Under UV illumination in both acidic and neutral-pH solutions, FeP nanoparticles deposited on TiO2 produced H2 at rates and amounts that begin to approach those of Pt/TiO2. FeP therefore is a highly Earth-abundant material for efficiently facilitating the HER both electrocatalytically and photocatalytically.

show abstract

Section: Resultsmentioning

confidence: 99%

Electrocatalytic and Photocatalytic Hydrogen Production from Acidic and Neutral-pH Aqueous Solutions Using Iron Phosphide Nanoparticles

et al. 2014

View full text Add to dashboard Cite

show abstract

“…Li is likely either intercalated into the Zn seeds or amorphous Sb. Powder XRD data of a '0 min' sample (removed and isolated immediately upon injection) does 55,[57][58][59][60][61][62][63] Scheme 2. Mechanism of formation h*-LiZnSb.…”

Section: Resultsmentioning

confidence: 99%

Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides

et al. 2018

View full text Add to dashboard Cite

Soft chemistry methods offer the possibility of synthesizing metastable and kinetic products that are unobtainable through thermodynamically-controlled, high-temperature reactions. A recent solution-phase exploration of Li-Zn-Sb phase space revealed a previously unknown cubic half-Heusler MgAgAs-type LiZnSb polytype. Interestingly, this new cubic phase was calculated to be the most thermodynamically stable, despite prior literature reporting only two other ternary phases (the hexagonal half-Heusler LiGaGe-type LiZnSb, and the full-Heusler Li2ZnSb). This surprising discovery, coupled with the intriguing optoelectronic and transport properties of many antimony containing Zintl phases, required a thorough exploration of syn-thetic parameters. Here, we systematically study the effects that different precursor concentrations, injection order, nucleation and growth temperatures, and reaction time have on the solution-phase synthesis of these materials. By doing so, we identify conditions that selectively yield several unique ternary (c-LiZnSb vs. h*-LiZnSb), binary (ZnSb vs. Zn8Sb7), and metallic (Zn, Sb) products. Further, we find one of the ternary phases adopts a variant of the previously observed hexagonal LiZnSb struc-ture. Our results demonstrate the utility of low temperature solution phase-soft synthesis-methods in accessing and mining a rich phase space. We anticipate that this work will motivate further exploration of multinary I-II-V compounds, as well as encourage similarly thorough investigations of related Zintl systems by solution phase methods. Disciplines Materials ChemistryComments "This document is the unedited Author's version of a Submitted Work that was subsequently accepted for publication in Chemistry of Materials, copyright © American Chemical Society after peer review. To access the final edited and published work see http://dx.doi.org/10.1021/acs.chemmater.8b02910. ABSTRACT: Soft chemistry methods offer the possibility of synthesizing metastable and kinetic products that are unobtainable through thermodynamically-controlled, high-temperature reactions. A recent solution-phase exploration of Li-Zn-Sb phase space revealed a previously unknown cubic half-Heusler MgAgAs-type LiZnSb polytype. Interestingly, this new cubic phase was calculated to be the most thermodynamically stable, despite prior literature reporting only two other ternary phases (the hexagonal half-Heusler LiGaGe-type LiZnSb, and the full-Heusler Li2ZnSb). This surprising discovery, coupled with the intriguing optoelectronic and transport properties of many antimony containing Zintl phases, required a thorough exploration of synthetic parameters. Here, we systematically study the effects that different precursor concentrations, injection order, nucleation and growth temperatures, and reaction time have on the solution-phase synthesis of these materials. By doing so, we identify conditions that selectively yield several unique ternary (c-LiZnSb vs. h*-LiZnSb), binary (ZnSb vs. Zn8Sb7), and metallic (Zn, Sb) products. Furt...

show abstract

“…Controlled compositions, i.e., metal-rich or phosphorus-rich, are achievable by varying the reaction time/ temperature or using inverse cannulation of metal-nanoparticle/hot TOP. [ 24 ] This was developed as a general approach for the synthesis of phosphides and is applicable to a wide range of transition metals, i.e., those with 3d, 4d, 5d structures including Ni 2 P, FeP, palladium phosphide, and platinum phosphide. The resultant nanoparticles/nanorods with a particle size ranging from several nm to ≈20 nm have attractive attributes of good uniformity and crystallinity, and the well-defi ned nanostructures are potentially ideal for electrocatalysis.…”

Section: Organic Phosphinementioning

confidence: 99%

A Review of Phosphide‐Based Materials for Electrocatalytic Hydrogen Evolution

Xiao

Chen

Wang

2015

Advanced Energy Materials

761

409

View full text Add to dashboard Cite

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...

show abstract

Control of Phase in Phosphide Nanoparticles Produced by Metal Nanoparticle Transformation: Fe₂P and FeP

Cited by 103 publications

References 28 publications

Electrocatalytic and Photocatalytic Hydrogen Production from Acidic and Neutral-pH Aqueous Solutions Using Iron Phosphide Nanoparticles

Electrocatalytic and Photocatalytic Hydrogen Production from Acidic and Neutral-pH Aqueous Solutions Using Iron Phosphide Nanoparticles

Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides

A Review of Phosphide‐Based Materials for Electrocatalytic Hydrogen Evolution

Contact Info

Product

Resources

About

Control of Phase in Phosphide Nanoparticles Produced by Metal Nanoparticle Transformation: Fe2P and FeP

Cited by 103 publications

References 28 publications

Electrocatalytic and Photocatalytic Hydrogen Production from Acidic and Neutral-pH Aqueous Solutions Using Iron Phosphide Nanoparticles

Electrocatalytic and Photocatalytic Hydrogen Production from Acidic and Neutral-pH Aqueous Solutions Using Iron Phosphide Nanoparticles

Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides

A Review of Phosphide‐Based Materials for Electrocatalytic Hydrogen Evolution

Contact Info

Product

Resources

About

Control of Phase in Phosphide Nanoparticles Produced by Metal Nanoparticle Transformation: Fe₂P and FeP