On the Effect of Cu on the Activity of Carbon Supported Ni Nanoparticles for Hydrogen Electrode Reactions in Alkaline Medium

Oshchepkov, Alexandr G.; Simonov, P.A.; Cherstiouk, Olga V.; Nazmutdinov, Renat R.; Glukhov, Dmitrii V.; Зайковский, В. И.; Kardash, T. Yu.; Kvon, Ren I.; Bonnefont, Antoine; Simonov, Alexandr N.; Parmon, Valentin N.; Savinova, Elena R.

doi:10.1007/s11244-015-0487-5

Cited by 50 publications

(51 citation statements)

References 37 publications

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“…Ac onsistent example is NiÀCu, which shows ag reater HER performance than Ni and Cu in alkaline conditions. [93][94][95][96][97] Another promising materiali sN i À Mo; [98][99][100][101] however,t here have been issues associated with its low dispersion of the actives urface. Ab reakthrough study in this context was reported in 2013, in which highly dispersed NiÀMo nanopowders were successfully prepared and utilized.…”

Section: Her At Extreme Ph:general Aspects and Introduction To The Inmentioning

confidence: 99%

Towards Versatile and Sustainable Hydrogen Production through Electrocatalytic Water Splitting: Electrolyte Engineering

2017

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Recent advances in power generation from renewable resources necessitate conversion of electricity to chemicals and fuels in an efficient manner. Electrocatalytic water splitting is one of the most powerful and widespread technologies. The development of highly efficient, inexpensive, flexible, and versatile water electrolysis devices is desired. This review discusses the significance and impact of the electrolyte on electrocatalytic performance. Depending on the circumstances under which the water splitting reaction is conducted, the required solution conditions, such as the identity and molarity of ions, may significantly differ. Quantitative understanding of such electrolyte properties on electrolysis performance is effective to facilitate the development of efficient electrocatalytic systems. The electrolyte can directly participate in reaction schemes (kinetics), affect electrode stability, and/or indirectly impact the performance by influencing the concentration overpotential (mass transport). This review aims to guide fine‐tuning of the electrolyte properties, or electrolyte engineering, for (photo)electrochemical water splitting reactions.

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Section: Her At Extreme Ph:general Aspects and Introduction To The Inmentioning

confidence: 99%

Towards Versatile and Sustainable Hydrogen Production through Electrocatalytic Water Splitting: Electrolyte Engineering

2017

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“…24 Such dissolution, deposition and HER catalysis has been previously proposed with nickel electrodes in acidic solutions, 43 and nickel in general has long been known to be a reasonably efficient catalyst for the hydrogen evolution reaction. [40][41][42][43] Ideally, electron microscopy techniques would be used to gather direct evidence of deposited particles, as in previous reports. [32][33][34][35] (Figure 3), ruling out electronic impacts of the anion on the NiO valence band.…”

Section: Discussionmentioning

confidence: 99%

“…Regarding the former case, metallic nickel has long been known as a reasonably efficient catalyst for the hydrogen evolution reaction. [40][41][42][43] Herein, the photo-electro-generation of H2 by PMA-6T-TPA-sensitized NiO photocathodes without intentionally-introduced HER catalysts is examined under a range of varying conditions to distinguish between the above possible mechanisms. The effects of pH, chemical nature of electrolyte, presence of admixtures in solutions, and the availability of the interfaces between unmodified, electrically disconnected NiO and adsorbed dye are examined.…”

Section: Introductionmentioning

confidence: 99%

Origin of Photoelectrochemical Generation of Dihydrogen by a Dye-Sensitized Photocathode without an Intentionally Introduced Catalyst

et al. 2017

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Dye-sensitized photocathodes have been observed on several occasions to sustain light-driven H 2 generation without intentionally introduced catalysts. Herein, plausible mechanisms addressing this phenomenon are probed by a combination of long-term photoelectrochemical measurements with concurrent gas chromatography, transient absorption spectroscopy, and inductively coupled mass spectrometry using a perylenemonoimide-sexithiophene-triphenylamine (PMI-6T-TPA) sensitized NiO electrode. The experimental evidence obtained discounts the possibility for direct reduction of hydrogen by the dye and demonstrates that the availability of interfaces between dye molecules and any electrically disconnected NiO particles exposed to the electrolyte solution is critical for photoelectrocatalytic H 2 generation. These interfaces are postulated to serve as photoactive sites for the formation of a hydrogen evolution catalyst, e.g., metallic nickel, which can accept photogenerated electrons from the excited dye molecules. The Ni 0 catalyst can form via photoelectroreduction of Ni 2+ , which has been found to slowly dissolve from the NiO support into the solutions during the photoelectrochemical measurements. Additionally, dependence of the H 2 generation rate on the anion within the electrolyte has been identified, with the highest rates of 35-40 nmol h -1 cm -2 achieved with acetate. The origin of this dependence remains unsolved at this stage but is clearly demonstrated to be not associated with the different rates of dissolution of NiO, the presence of other transition metal contaminants, nor electronic impacts of the anion on the NiO valence band. Overall, the results herein demonstrate that the effects of the chemical nature of the electrolyte, metallic nickel deposited from dissolved Ni 2+ , and availability of the interfaces between disconnected NiO and adsorbed dye should be considered when interpreting the photoelectrocatalytic performance of dye-sensitized photocathodes for dihydrogen evolution. × Our colleague, mentor and friend Prof. Leone Spiccia has passed away before this work could be published. Leone was an outstanding researcher and personality, and is sadly missed. ABSTRACTDye-sensitized photocathodes have been observed on several occasions to sustain light-driven H2 generation without intentionally-introduced catalysts. Herein, plausible mechanisms addressing this phenomenon are probed by a combination of long-term photo-electrochemical measurements with concurrent gas chromatography, transient absorption spectroscopy and inductively coupled mass spectrometry using a perelenmonoimid-sexithiophene-triphenylamine (PMI-6T-TPA) sensitized NiO electrode. The experimental evidence obtained discounts the possibility for direct reduction of hydrogen by the dye and demonstrates that the availability of interfaces between dye molecules and any electrically-disconnected NiO particles exposed to the electrolyte solution is critical for photo-electrocatalytic H2 generation. These interfaces are postulated to serve as photo-a...

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“…[25] In agreement with the previous publications, HOR/HER kinetics is significantly improved when the Ni electrode surface is partially covered with Ni (hydr)oxide species [35] and/or when Ni is alloyed with Cu. [40,41] The CV curves obtained on partially oxidized Ni disk and on NiCu/C electrodes at pH 12, 13 and 14 are displayed in Figure 2a,b and 3, respectively. The partially electrochemically (EC)oxidized Ni sample was prepared by applying three potential cycles between À 0.30 and 1.0 V, causing the formation of Ni (hydr)oxide.…”

Section: Influence Of Ph On the Kinetics Of The Hydrogen Electrode Rementioning

confidence: 99%

“…Since the HOR/HER activity of Ni is rather low [29][30][31] due to the strong hydrogen binding to the surface, [32][33][34] it is usually enhanced either by partially oxidizing Ni surfaces [21,[35][36][37][38] or by combining Ni with other non-noble transition metals such as Mo, Cr, Co or Cu. [34,[39][40][41][42][43][44] Hence, to have a better understanding of the pH dependence, along with metallic Ni, in this work we also explore a partially oxidized Ni as well as a NiCu/C electrode. Measurements are performed in 0.01 M, 0.1 M and 1 M NaOH solutions without addition of another supporting electrolyte to avoid the presence of anions, which might adsorb on the Ni surface and affect the HOR and HER currents.…”

Section: Introductionmentioning

confidence: 99%

Influence of the NaOH Concentration on the Hydrogen Electrode Reaction Kinetics of Ni and NiCu Electrodes

et al. 2020

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Nickel is a promising electrocatalyst for hydrogen electrode reactions in alkaline media. Its electrocatalytic activity for hydrogen oxidation and evolution reactions can be enhanced when its surface is partially covered by Ni (hydr)oxides or by associating it with Cu. In this work, the influence of the NaOH concentration on the hydrogen electrode kinetics on various Ni electrodes is investigated. On metallic Ni, the electrocatalytic activity (measured as an exchange current density normalized to the surface area of Ni) is almost constant between pH 12 and 14, whereas it decreases by a factor of two on partially oxidized Ni and on the NiCu/C electrode. Analyzing the current potential curves with the help of microkinetic modeling reveals that the Had and OHad binding energies on Ni do not depend on pH, whereas the rate constants of the Volmer and Heyrovsky reactions decrease with pH. The pH effect on the electron transfer elementary act is briefly discussed in the framework of a quantum mechanical theory.

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On the Effect of Cu on the Activity of Carbon Supported Ni Nanoparticles for Hydrogen Electrode Reactions in Alkaline Medium

Cited by 50 publications

References 37 publications

Towards Versatile and Sustainable Hydrogen Production through Electrocatalytic Water Splitting: Electrolyte Engineering

Towards Versatile and Sustainable Hydrogen Production through Electrocatalytic Water Splitting: Electrolyte Engineering

Origin of Photoelectrochemical Generation of Dihydrogen by a Dye-Sensitized Photocathode without an Intentionally Introduced Catalyst

Influence of the NaOH Concentration on the Hydrogen Electrode Reaction Kinetics of Ni and NiCu Electrodes

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