Cost-effective synthesis of carbon loaded Co3O4 for controlled hydrogen generation via NaBH4 hydrolysis

Ugale, Ashok D.; Ghodke, Neha P.; Kang, Gil–Seon; Nam, Ki-Bong; Bhoraskar, S. V.; Mathe, V. L.; Yoo, Ji Beom

doi:10.1016/j.ijhydene.2021.09.262

Cited by 35 publications

(6 citation statements)

References 49 publications

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“…Figure 4(d) further unveils that nearly 100 % of H 2 generation efficiencies could be afforded, even at high NaBH 4 concentration (i. e., 175 mM) meanwhile the calculated H 2 generation rates were comparable, which is in agreement with the result in Figure 4(c). Since increased NaBH 4 concentrations would generate more by‐products (e. g., NaBO 2 ), capable of blocking the active sites of the catalyst as well as enhancing the solution viscosity, [11a,24] this result demonstrates the excellent durability of HCSCO towards catalytic hydrolysis of NaBH 4 .…”

Section: Resultsmentioning

confidence: 89%

“…Dou and his co‐colleagues prepared PdO‐Co 3 O 4 composite and used it for H 2 generation from NaBH 4 hydrolysis, in which PdO‐Co 3 O 4 catalyst has an exceptional turnover frequency (3325.6 mol H2 min −1 mol Pd −1 ) and low activation energy (43.2 kJ mol −1 ) [13] . Many other studies in the literature also aimed to develop noble metal doped cobalt oxide composites as reported elsewhere [11a,14] . Even though these catalysts could enhance the H 2 generation effectiveness, noble metals are still needed.…”

Section: Introductionmentioning

confidence: 99%

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MOF‐Templated Hierarchical Porous Hollow Core‐Shell Framework Cobalt Oxide for Enhancing Hydrogen Generation from Borohydride‐Based Hydrolysis

Tran,

Van,

Tsai

et al. 2023

ChemCatChem

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Designing and fabricating a competent cobalt‐based catalyst for sodium borohydride (NaBH4) hydrolysis is of great importance. The present work reports the synthesis of hierarchical porous hollow core‐shell framework cobalt oxide (HCSCO) via etching and calcination processes, which is then employed for catalyzing NaBH4 hydrolysis. Various characterization analyses have been employed to reveal the surficial morphology, the hollow core‐shell framework, the crystalline structure, the fruiful formation of Co3O4, the porosity, and the chemical states of HCSCO. The as‐prepared HCSCO showed prominent catalytic hydrolysis of NaBH4 to generate H2 with a H2 generation rate of 441 ml min‐1 gcatalyst‐1 and a low activation energy (Ea) of 34.8 kJ mol‐1. This Ea value of HCSCO is substantially lower than that of other catalysts, including noble metal catalysts or composites reported in the literature. Besides, HCSCO could remain its superb activity (~100% H2 generation efficiency) over multiple hydrolysis cycles without significant changes of morphology and microstructure. The catalytic hydrolysis mechanism for H2 generation from NaBH4 using HCSCO is also proposed. This work provides a valuable strategy for the synthesis and fabrication of state‐of‐art catalysts for H2 generation from the hydrolysis of NaBH4.

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Section: Resultsmentioning

confidence: 89%

Section: Introductionmentioning

confidence: 99%

MOF‐Templated Hierarchical Porous Hollow Core‐Shell Framework Cobalt Oxide for Enhancing Hydrogen Generation from Borohydride‐Based Hydrolysis

Tran,

Van,

Tsai

et al. 2023

ChemCatChem

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“…With a hydrogen storage capacity of 10.6 wt.%, NaBH 4 is a valuable reducing reagent used in organic synthesis and decomposes at a high temperature typical of ionic compounds like metal salts (534 °C) [ 370 , 371 , 372 , 373 , 374 ]. The synthesis was reported first by Schlesinger, who reacted trimethyl borate with sodium hydride in hydrocarbon oil, at boiling point (250 °C) (Equation (90)) [ 375 ].…”

Section: Model Systems For Hydrogen Storage Of Mbh and Other Rmh (Rea...mentioning

confidence: 99%

Complex Metal Borohydrides: From Laboratory Oddities to Prime Candidates in Energy Storage Applications

Comănescu

2022

Materials

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Despite being the lightest element in the periodic table, hydrogen poses many risks regarding its production, storage, and transport, but it is also the one element promising pollution-free energy for the planet, energy reliability, and sustainability. Development of such novel materials conveying a hydrogen source face stringent scrutiny from both a scientific and a safety point of view: they are required to have a high hydrogen wt.% storage capacity, must store hydrogen in a safe manner (i.e., by chemically binding it), and should exhibit controlled, and preferably rapid, absorption–desorption kinetics. Even the most advanced composites today face the difficult task of overcoming the harsh re-hydrogenation conditions (elevated temperature, high hydrogen pressure). Traditionally, the most utilized materials have been RMH (reactive metal hydrides) and complex metal borohydrides M(BH4)x (M: main group or transition metal; x: valence of M), often along with metal amides or various additives serving as catalysts (Pd2+, Ti4+ etc.). Through destabilization (kinetic or thermodynamic), M(BH4)x can effectively lower their dehydrogenation enthalpy, providing for a faster reaction occurring at a lower temperature onset. The present review summarizes the recent scientific results on various metal borohydrides, aiming to present the current state-of-the-art on such hydrogen storage materials, while trying to analyze the pros and cons of each material regarding its thermodynamic and kinetic behavior in hydrogenation studies.

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“…In most cases, the literature presents data on the high Co 3 O 4 activity in SBH hydrolysis [17][18][19][20][21][22]. In the reaction medium of such a strong reducing agent, in situ activation of Co 3 O 4 occurs through its partial reduction, forming catalytically active centers.…”

Section: Introductionmentioning

confidence: 99%

Co and Co3O4 in the Hydrolysis of Boron-Containing Hydrides: H2O Activation on the Metal and Oxide Active Centers

Butenko,

Komova,

Simagina

et al. 2024

Materials

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This work focuses on the comparison of H2 evolution in the hydrolysis of boron-containing hydrides (NaBH4, NH3BH3, and (CH2NH2BH3)2) over the Co metal catalyst and the Co3O4-based catalysts. The Co3O4 catalysts were activated in the reaction medium, and a small amount of CuO was added to activate Co3O4 under the action of weaker reducers (NH3BH3, (CH2NH2BH3)2). The high activity of Co3O4 has been previously associated with its reduced states (nanosized CoBn). The performed DFT modeling shows that activating water on the metal-like surface requires overcoming a higher energy barrier compared to hydride activation. The novelty of this study lies in its focus on understanding the impact of the remaining cobalt oxide phase. The XRD, TPR H2, TEM, Raman, and ATR FTIR confirm the formation of oxygen vacancies in the Co3O4 structure in the reaction medium, which increases the amount of adsorbed water. The kinetic isotopic effect measurements in D2O, as well as DFT modeling, reveal differences in water activation between Co and Co3O4-based catalysts. It can be assumed that the oxide phase serves not only as a precursor and support for the reduced nanosized cobalt active component but also as a key catalyst component that improves water activation.

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Cost-effective synthesis of carbon loaded Co3O4 for controlled hydrogen generation via NaBH4 hydrolysis

Cited by 35 publications

References 49 publications

MOF‐Templated Hierarchical Porous Hollow Core‐Shell Framework Cobalt Oxide for Enhancing Hydrogen Generation from Borohydride‐Based Hydrolysis

MOF‐Templated Hierarchical Porous Hollow Core‐Shell Framework Cobalt Oxide for Enhancing Hydrogen Generation from Borohydride‐Based Hydrolysis

Complex Metal Borohydrides: From Laboratory Oddities to Prime Candidates in Energy Storage Applications

Co and Co3O4 in the Hydrolysis of Boron-Containing Hydrides: H2O Activation on the Metal and Oxide Active Centers

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