Recent developments of transition metal phosphides as catalysts in the energy conversion field

Pei, Yu; Cheng, Yu; Chen, Jiyi; Smith, W. M.; Dong, Pei; Ajayan, Pulickel M.; Ye, Mingxin; Shen, Jianfeng

doi:10.1039/c8ta09454c

Cited by 213 publications

(135 citation statements)

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“…When used as catalytic materials, metal-rich phosphides show excellent activity in hydrogenation reactions. The nature, structure and synthesis of phosphides have been described in a number of reviews [17][18][19][20][21][22].…”

Section: Metal Phosphides and Catalysismentioning

confidence: 99%

Transition Metal Phosphides for the Catalytic Hydrodeoxygenation of Waste Oils into Green Diesel

2019

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Recently, catalysts based on transition metal phosphides (TMPs) have attracted increasing interest for their use in hydrodeoxygenation (HDO) processes destined to synthesize biofuels (green or renewable diesel) from waste vegetable oils and fats (known as hydrotreated vegetable oils (HVO)), or from bio-oils. This fossil-free diesel product is produced completely from renewable raw materials with exceptional quality. These efficient HDO catalysts present electronic properties similar to noble metals, are cost-efficient, and are more stable and resistant to the presence of water than other classical catalytic formulations used for hydrotreatment reactions based on transition metal sulfides, but they do not require the continuous supply of a sulfide source. TMPs develop a bifunctional character (metallic and acidic) and present tunable catalytic properties related to the metal type, phosphorous-metal ratio, support nature, texture properties, and so on. Here, the recent progress in TMP-based catalysts for HDO of waste oils is reviewed. First, the use of TMPs in catalysis is addressed; then, the general aspects of green diesel (from bio-oils or from waste vegetable oils and fats) production by HDO of nonedible oil compounds are presented; and, finally, we attempt to describe the main advances in the development of catalysts based on TMPs for HDO, with an emphasis on the influence of the nature of active phases and effects of phosphorous, promoters, and preparation methods on reactivity.

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Section: Metal Phosphides and Catalysismentioning

confidence: 99%

Transition Metal Phosphides for the Catalytic Hydrodeoxygenation of Waste Oils into Green Diesel

2019

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“…To achieve facile kinetics for both the Volmer and Heyrovsky-Tafel steps, modification of the surface structure and tuning of the electronic properties through transition metal doping is recommended as an important strategy.and Ni 2 P [18-20] have been regarded as very promising electrocatalysts for the HER owing to their low-cost, appropriate electronic structures, and high electrochemical stability. Nickel phosphide (Ni 2 P) in particular is an emerging catalyst for hydrogen evolution reactions [20][21][22][23], hydrodesulfurization (HDS) [24,25], hydrodenitrogenation (HDN) [26][27][28], hydrodeoxygenation (HDO) [29], hydrodechlorination (HDCl) [30], and water-gas shift reactions [31]. Ni 2 P is considered an attractive alternative to noble metal catalysts for HER [20] because both of its constituent elements nickel and phosphorous are cheap, abundant, and non-toxic, which makes Ni 2 P a promising cost-effective material for scalable renewable energy conversion systems.Nickel phosphides are stable and durable in strong acid and alkali conditions, prolonging the turnover number (TON) and lifetime of the catalyst and hence can achieve enhanced HER efficiency [32,33].…”

mentioning

confidence: 99%

First-Principles Mechanistic Insights into the Hydrogen Evolution Reaction on Ni2P Electrocatalyst in Alkaline Medium

Cross

Dzade

2020

Catalysts

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Nickel phosphide (Ni 2 P) is a promising material for the electrocatalytic generation of hydrogen from water. Here, we present a chemical picture of the fundamental mechanism of Volmer-Tafel steps in hydrogen evolution reaction (HER) activity under alkaline conditions at the (0001) and (1010) surfaces of Ni 2 P using dispersion-corrected density functional theory calculations. Two terminations of each surface (Ni 3 P 2 -and Ni 3 P-terminated (0001); and Ni 2 P-and NiP-terminated (1010)), which have been shown to coexist in Ni 2 P samples depending on the experimental conditions, were studied. Water adsorption on the different terminations of the Ni 2 P (0001) and (1010) surfaces is shown to be exothermic (binding energy in the range of 0.33−0.68 eV) and characterized by negligible charge transfer to/from the catalyst surface (0.01−0.04 e − ). High activation energy barriers (0.86−1.53 eV) were predicted for the dissociation of water on each termination of the Ni 2 P (0001) and (1010) surfaces, indicating sluggish kinetics for the initial Volmer step in the hydrogen evolution reaction over a Ni 2 P catalyst. Based on the predicted Gibbs free energy of hydrogen adsorption (∆G H *) at different surface sites, we found that the presence of Ni 3 -hollow sites on the (0001) surface and bridge Ni-Ni sites on the (1010) surface bind the H atom too strongly. To achieve facile kinetics for both the Volmer and Heyrovsky-Tafel steps, modification of the surface structure and tuning of the electronic properties through transition metal doping is recommended as an important strategy.and Ni 2 P [18-20] have been regarded as very promising electrocatalysts for the HER owing to their low-cost, appropriate electronic structures, and high electrochemical stability. Nickel phosphide (Ni 2 P) in particular is an emerging catalyst for hydrogen evolution reactions [20][21][22][23], hydrodesulfurization (HDS) [24,25], hydrodenitrogenation (HDN) [26][27][28], hydrodeoxygenation (HDO) [29], hydrodechlorination (HDCl) [30], and water-gas shift reactions [31]. Ni 2 P is considered an attractive alternative to noble metal catalysts for HER [20] because both of its constituent elements nickel and phosphorous are cheap, abundant, and non-toxic, which makes Ni 2 P a promising cost-effective material for scalable renewable energy conversion systems.Nickel phosphides are stable and durable in strong acid and alkali conditions, prolonging the turnover number (TON) and lifetime of the catalyst and hence can achieve enhanced HER efficiency [32,33]. The Ni 2 P (0001) surface is the most studied facet for HER activity owing to its comparable predicted hydrogen evolution activity to that of hydrogenase [22,[34][35][36]. Earlier investigations have considered HER activity in acidic medium over Ni 2 P catalysts, whereby the Volmer-Tafel mechanism (H + (aq) → H * , 2H * → ↑H 2 ) involves only characterizing the Gibb's free energy hydrogen adsorption to the catalyst surface [22,23]. There exist limited studies of the HER activity of Ni 2 P under alkaline c...

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“…Moreover, EIS was also carried out at an overpotential of 0 V from 100 kHz to 0.01 Hz in 1 m KOH. As is shown in Figure f, the semicircles in the high‐ and low‐frequency range of the Nyquist plots are attributed to the charge‐transfer resistance ( R ct ) and solution resistance ( R s ), respectively . The smallest R ct of CuCo 2 ‐P and CuCo‐P (2.5 Ω) were achieved compared to that of CuCo 3 ‐P (3.5 Ω) and CoP 3 (7 Ω), indicating the faster HER kinetic and expedited Faradaic process.…”

Section: Resultsmentioning

confidence: 88%

Precursor‐Transformation Strategy Preparation of CuP_x Nanodots–Decorated CoP₃ Nanowires Hybrid Catalysts for Boosting pH‐Universal Electrocatalytic Hydrogen Evolution

Cheng

Pei

Zhuang

et al. 2019

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The development of earth‐abundant, low cost, and versatile electrocatalysts for producing hydrogen from water electrolysis is still challenging. Herein, based on high hydrogen evolution reaction (HER) activity of transition metal phosphides, a CoP3 nanowire decorated with copper phosphides (denoted as CuPx) nanodots structures synthesized through a simple and easily scalable precursor‐transformation strategy is reported as a highly efficient HER catalyst. By decorating with CuPx nanodots, the optimized CoP3 nanowires electrode exhibits excellent catalytic activity and long‐term durability for HER in alkaline conditions, achieving a low overpotential of 49.5 mV at a geometrical catalytic current density of 10 mA cm−2 with a small Tafel slope of 58.0 mV dec−1, while also performing quite well in neutral and acidic media. Moreover, its overall performance exceeds most of the reported state‐of‐the‐art catalysts, especially under high current density of 100 mA cm−2, demonstrating its potential as a promising versatile pH universal electrocatalyst for efficient water electrolysis. These results indicate that the incorporation of earth‐abundant stable element copper can significantly enhance catalytic activity, which widens the application range of copper and provides a new path for design and selection of HER catalysts.

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Recent developments of transition metal phosphides as catalysts in the energy conversion field

Abstract: Catalysts play an important role in the energy conversion reaction process.

Cited by 213 publications

References 215 publications

Transition Metal Phosphides for the Catalytic Hydrodeoxygenation of Waste Oils into Green Diesel

Transition Metal Phosphides for the Catalytic Hydrodeoxygenation of Waste Oils into Green Diesel

First-Principles Mechanistic Insights into the Hydrogen Evolution Reaction on Ni2P Electrocatalyst in Alkaline Medium

Precursor‐Transformation Strategy Preparation of CuP_x Nanodots–Decorated CoP₃ Nanowires Hybrid Catalysts for Boosting pH‐Universal Electrocatalytic Hydrogen Evolution

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Recent developments of transition metal phosphides as catalysts in the energy conversion field

Abstract: Catalysts play an important role in the energy conversion reaction process.

Cited by 213 publications

References 215 publications

Transition Metal Phosphides for the Catalytic Hydrodeoxygenation of Waste Oils into Green Diesel

Transition Metal Phosphides for the Catalytic Hydrodeoxygenation of Waste Oils into Green Diesel

First-Principles Mechanistic Insights into the Hydrogen Evolution Reaction on Ni2P Electrocatalyst in Alkaline Medium

Precursor‐Transformation Strategy Preparation of CuPx Nanodots–Decorated CoP3 Nanowires Hybrid Catalysts for Boosting pH‐Universal Electrocatalytic Hydrogen Evolution

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Precursor‐Transformation Strategy Preparation of CuP_x Nanodots–Decorated CoP₃ Nanowires Hybrid Catalysts for Boosting pH‐Universal Electrocatalytic Hydrogen Evolution