Polythiophene‐Assisted Vapor Phase Synthesis of Carbon Nanotube‐Supported Rhodium Sulfide as Oxygen Reduction Catalyst for HCl Electrolysis

Jin, Chen; Nagaiah, Tharamani C.; Xia, Wei; Bron, Michael; Schuhmann, Wolfgang

doi:10.1002/cssc.201000315

Cited by 13 publications

(9 citation statements)

References 23 publications

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“…It is noted that this high crystallinity is difficult to achieve by other methods at such low temperature, because reaction between Rh and element sulfur is normally of low activity, which usually require a temperature higher than 700 C through solid reaction. 11,12,25 The broadening of diffraction peaks demonstrates that the crystal size is in nanometer range. As measured from Scherrer equation, the crystallite size is 8.2 AE 1.6 nm.…”

Section: Structure Features and Morphologymentioning

confidence: 99%

“…Rhodium suldes are gaining signicant attention because of the prospects as catalysts in hydrodesulfurization, 1,2 photochemical decomposition of aqueous sulde 3 and in oxygen reduction reaction (ORR) for fuel cells and electrolysis. [4][5][6][7][8][9][10][11] In the particular case of hydrochloric acid electrolysis, Pt, known as the most effective catalyst for ORR, has been shown to be of poor stability in the highly corrosive conditions of hydrochloric acid and be constantly poisoned by dissolved chloride ions and various dissolved organic contaminants in the electrolyte in which its electrocatalytic performance would be readily and substantially deteriorated. In contrast, rhodium suldes are relatively unaffected by chloride ions and organic contaminants.…”

Section: Introductionmentioning

confidence: 99%

“…In the past years, literature sources have demonstrated that rhodium chalcogenides are active and highly stable catalysts for ORR in depolarized electrolysis of hydrochloric acid. 6,7,11 Rhodium sulde consists of three different crystal phases, Rh 2 S 3 , Rh 17 S 15 , and Rh 3 S 4 . They were conventionally synthesized in bulk via a high temperature reaction over 700 C from the respective elements in a sealed quartz tube.…”

Section: Introductionmentioning

confidence: 99%

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In situ synthesis of well crystallized rhodium sulfide/carbon composite nanospheres as catalyst for hydrochloric acid electrolysis

Yanagisawa

et al. 2014

J. Mater. Chem. A

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Rhodium sulfide/carbon nanocomposites were synthesized via a one-step alcohol-thermal method at 400 C from Rh 6 (CO) 16 and elemental S. Characterizations by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy revealed that the products were composed of amorphous carbon with spherical morphology and numerous highly crystallized Rh 2 S 3 /Rh 17 S 15 nanocrystals, presented as uniform size composite nanospheres of 45-90 nm diameter. The crystallographic composition of rhodium sulfide in those composites depended on the initial S/Rh molar ratio and utilized solvent. Such hybrid nanomaterials displayed good dispersion of the rhodium sulfide nanoparticles, high surface area and extraordinary thermal/chemical resistance, making them attractive materials for electrocatalytic application of HCl electrolysis. Cyclic voltammetry and rotating disk electrode measurements were employed to evaluate the catalytic performance for oxygen reduction reaction in HCl electrolysis. It was illustrated that all rhodium sulfide/carbon nanocomposites were active towards oxygen reduction reaction. Especially, the catalyst synthesized in ethanol containing Rh 17 S 15 phase outperformed commercial Pt/C in stability. Recently, our group reported hydrothermal and xylenethermal synthesis of rhodium suldes. 24,25 Both methods led to well-crystallized Rh 2 S 3 or Rh 17 S 15 phase, depending on the initial S/Rh molar ratio in the raw materials. The solvothermal reaction conducted in xylene gives rise to products with higher

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Section: Structure Features and Morphologymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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In situ synthesis of well crystallized rhodium sulfide/carbon composite nanospheres as catalyst for hydrochloric acid electrolysis

Yanagisawa

et al. 2014

J. Mater. Chem. A

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“…Though, the exponential increase in the cost of the metal have been counterbalanced by the decrease in the metal content [16] with additional carbon supports but these carbon materials render a poor stability due to corrosion under oxidative environments affecting the operational durability of catalysts [17] . Thus, designing of catalyst with both ample abundance and longer durability for HCl electrolysis is highly desirable [18,19] . Nevertheless, only few reports are available as bifunctional catalyst on non‐noble metals viz ., Fe−N−C [20] and recently we have reported molecular catalyst [21] and Co‐NSC [22] as a catalyst towards ODC and chlorine production.…”

Section: Introductionmentioning

confidence: 99%

Recovery of High Purity Chlorine by Cu‐Doped Fe₂O₃ in Nitrogen Containing Carbon Matrix: A Bifunctional Electrocatalyst for HCl Electrolysis

et al. 2021

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An environmentally benign approach towards synthesis of a non‐noble metal and/or metal oxide doped incorporated in nitrogen containing carbon matrix (Cu−Fe2O3/NC) is premeditated in this study. In‐situ incorporation of Cu, Fe2O3 as well as nitrogen into the carbon matrix using a single gel precursor simplified the synthetic route and divulged bifunctional activity assisting chlorine evolution at anode and oxygen reduction reaction at cathodic counterpart during HCl electrolysis. As a result of synergy between Cu and Fe2O3 in N‐ doped carbon matrix, enhanced activity and stability is stimulated. Catalyst optimization was executed by varying the weight percentage of metal reactants added during precursor synthesis (2, 5 and 10 wt. %), which rendered different composition of Cu, Fe2O3 and N in the composite with flake‐like morphology at same thermal treatment conditions. Electrochemical studies were performed in 0.4 M HCl analogous to industrial waste HCl, to investigate the bifunctional activity of catalyst where Cu−Fe2O3 (5 %)/NC came out to be the most active and exhibited long term stability for 24 hours at onset potential of chlorine evolution. It offered a higher current density of 92.1 mA cm−2 at 1.7 V vs. RHE during chlorine evolution and comparable activity to that of benchmark noble metal based catalyst along with more positive onset potential and high diffusion limiting current density of 0.78 V vs. RHE and 6 mA cm−2 during oxygen reduction respectively.

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“…Rhodium sulfide catalysts have shown promise in applications for hydro-desulfurization, [8][9] photochemical decomposition of aqueous sulfide 10 and the oxygen reduction reaction (ORR) for fuel cells and electrolysis. [11][12][13][14][15][16][17][18] In the particular case of hydrochloric acid electrolysis, Pt, known as the most effective catalyst for non-chloride systems, has been shown to have poor stability in the highly corrosive conditions of hydrochloric acid and be constantly poisoned by chloride ions. In contrast, rhodium sulfides are relatively unaffected by chloride ions.…”

mentioning

confidence: 99%

A Rh_xS_y/C Catalyst for the Hydrogen Oxidation and Hydrogen Evolution Reactions in HBr

Masud

Nguyen

Singh

et al. 2015

J. Electrochem. Soc.

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Rhodium sulfide (Rh 2 S 3 ) on carbon support was synthesized by refluxing rhodium chloride with ammonium thiosulfate. Thermal treatment of Rh 2 S 3 at high temperatures (600 • C to 850 • C) in presence of argon resulted in the transformation of Rh 2 S 3 into Rh 3 S 4 , Rh 17 S 15 and Rh which were characterized by TGA/DTA, XRD, EDX, and deconvolved XPS analyses. The catalyst particle size distribution ranged from 3 to 12 nm. Cyclic voltammetry and rotating disk electrode measurements were used to evaluate the catalytic activity for hydrogen oxidation and evolution reactions in H 2 SO 4 and HBr solutions. The thermally treated catalysts show high activity for the hydrogen reactions. The exchange current densities (i o ) of the synthesized Rh x S y catalysts in H 2 -saturated 1M H 2 SO 4 and 1M HBr for HER and HOR were 0.9 mA/cm 2 to 1.0 mA/cm 2 and 0.8 to 0.9 mA/cm 2 , respectively. The intermittent availability of renewable electricity from solar and wind sources has increased significantly.1 To match their often unpredictable power generation cycles with demand, low cost electrical energy storage systems are required.A flow battery/regenerative fuel cell is an electrochemical storage device that stores the electrical energy as chemical energy in a fuel and converts the chemical energy of the fuel directly back to electrical energy. The potentially low cost and relatively rapid process of electrical-to-chemical or chemical-to-electrical energy, in comparison to the slower mechanical-to-electrical energy processes used with flywheel and compressed air storage, offers unique advantages. The discharge cycle of the flow battery utilizes a fuel cell which has proven to be efficient and clean devices for energy conversion. Fuel cells are regarded by some as the energy conversion devices of the future and provide a faster, cleaner, more efficient, and possibly more flexible chemical-to-electrical energy conversion platform than present combustion based systems. [2][3][4] In comparison to other flow battery systems, the regenerative hydrogen-bromine fuel cell has advantages including high round-trip energy conversion efficiency, high power density and storage capacity, fast kinetics of both hydrogen and bromine electrode reactions, low cost active materials, simplicity and reliability. [5][6] The core component of a H 2 /Br 2 regenerative fuel cell system is an acid-based H 2 /Br 2 fuel cell. The charge and discharge reactions occurring in the fuel cell are as follows. At the bromine electrode, during the charge cycle, bromide ions in an HBr solution are oxidized to form bromine and two electrons; require a catalyst that is highly active, to keep the performance high and the cost low, stable and durable in the highly corrosive HBr/Br 2 environment of the cell as required by the extended life of this application. During the operation of a H 2 -Br 2 fuel cell, HBr and Br 2 could cross from the bromine side through the proton conducting membrane to the hydrogen side potentially leading to the corrosion and poisoning of th...

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Polythiophene‐Assisted Vapor Phase Synthesis of Carbon Nanotube‐Supported Rhodium Sulfide as Oxygen Reduction Catalyst for HCl Electrolysis

Cited by 13 publications

References 23 publications

In situ synthesis of well crystallized rhodium sulfide/carbon composite nanospheres as catalyst for hydrochloric acid electrolysis

In situ synthesis of well crystallized rhodium sulfide/carbon composite nanospheres as catalyst for hydrochloric acid electrolysis

Recovery of High Purity Chlorine by Cu‐Doped Fe₂O₃ in Nitrogen Containing Carbon Matrix: A Bifunctional Electrocatalyst for HCl Electrolysis

A Rh_xS_y/C Catalyst for the Hydrogen Oxidation and Hydrogen Evolution Reactions in HBr

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Polythiophene‐Assisted Vapor Phase Synthesis of Carbon Nanotube‐Supported Rhodium Sulfide as Oxygen Reduction Catalyst for HCl Electrolysis

Cited by 13 publications

References 23 publications

In situ synthesis of well crystallized rhodium sulfide/carbon composite nanospheres as catalyst for hydrochloric acid electrolysis

In situ synthesis of well crystallized rhodium sulfide/carbon composite nanospheres as catalyst for hydrochloric acid electrolysis

Recovery of High Purity Chlorine by Cu‐Doped Fe2O3 in Nitrogen Containing Carbon Matrix: A Bifunctional Electrocatalyst for HCl Electrolysis

A RhxSy/C Catalyst for the Hydrogen Oxidation and Hydrogen Evolution Reactions in HBr

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Recovery of High Purity Chlorine by Cu‐Doped Fe₂O₃ in Nitrogen Containing Carbon Matrix: A Bifunctional Electrocatalyst for HCl Electrolysis

A Rh_xS_y/C Catalyst for the Hydrogen Oxidation and Hydrogen Evolution Reactions in HBr