Cobalt borate catalysts for hydrogen production via hydrolysis of sodium borohydride

Ozerova, Anna M.; Симагина, В.И.; Komova, O.V.; Netskina, O.V.; Одегова, Г. В.; Булавченко, О. А.; Рудина, Н. А.

doi:10.1016/j.jallcom.2011.10.033

Cited by 73 publications

(28 citation statements)

References 44 publications

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“…In many studies, it has been reported that cobalt catalysts produced from CoCl 2 were the most active catalysts for this reaction [17]. In addition to cobalt boride, cobalt borates have been also reported as the active catalyst [20,21]. In addition to cobalt boride, cobalt borates have been also reported as the active catalyst [20,21].…”

Section: Introductionmentioning

confidence: 98%

“…Liu et al reported that CoCl 2 was reacting with NaBH 4 , and the product of this reaction was cobalt boride, which was also an active catalyst for the NaBH 4 hydrolysis reaction [16]. In addition to cobalt boride, cobalt borates have been also reported as the active catalyst [20,21]. The boride and borate catalysts are called 'Co-B' catalysts [17,19].…”

Section: Introductionmentioning

confidence: 99%

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Catalytic hydrolysis of sodium borohydride on Co catalysts

Inokawa

Driss

Trovela

et al. 2016

Int. J. Energy Res.

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Summary The addition of NaBH4 to Co–ethylenediaminetetraacetate (Co–EDTA) and Co–citrate solutions at 25 °C does not lead to generation of hydrogen. However, in the presence of Co‐based catalysts synthesized via chemical reduction of Co–EDTA and Co–citrate complexes with NaBH4 at elevated temperature, an intensive generation of H2 took place. In this study, the reduction mechanism of both complexes was elucidated by using various techniques. From the results of attenuated total reflection and mass spectrometry analysis, it was suggested that NaBH4 was oxidized to NaBO2 and that organic ligands of Co complexes were decomposed to gaseous hydrocarbons, such as C2H4, C3H4, and/or C2H3N. Structural characterizations of X‐ray diffraction, scanning transmission electron microscopy, transmission electron microscope, energy‐dispersive spectroscopy, and X‐ray photoelectron spectra on the catalysts revealed that Co(OH)2, metallic cobalt, and cobalt borate were obtained in both cases. The morphology of Co(OH)2 and the dispersion of metallic cobalt and cobalt borate nanoparticles were significantly different. In the case of the catalyst prepared from Co–EDTA, the nanoparticles of Co species aggregated with diameters from 100 to several hundred nanometers on Co(OH)2 slabs. On the catalyst prepared from Co–citrate, the Co(OH)2 formed sheets, and the nanoparticles of Co species formed clusters of 5–10 nm in diameter, which are dispersed well on the Co(OH)2 sheet. The catalyst obtained from Co–citrate showed higher catalytic activity on hydrolysis reaction of NaBH4 than that from Co–EDTA. Copyright © 2016 John Wiley & Sons, Ltd.

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Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Catalytic hydrolysis of sodium borohydride on Co catalysts

Inokawa

Driss

Trovela

et al. 2016

Int. J. Energy Res.

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“…[1][2][3][4] Recently, first row transition metal borates have emerged as dioxygen (O 2 ) evolution catalysts, [5][6][7][8][9][10][11][12][13][14][15][16] cathode materials in lithium ion batteries, [17][18][19][20][21][22] catalysts for H 2 production by hydrolysis of sodium borohydride, 23 and superhydrophilic Ni 3 (BO 3 ) 2 layers. 24 For many applications, metal borates must be grown as thin films.…”

Section: Introductionmentioning

confidence: 99%

“…34 ALD growth from various bimetallic precursors does not generally replicate the precursor element stoichiometries in the resultant thin films. [35][36][37][38] Given the increasing importance of first row transition metal borates, [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] proposed to arise from the strong oxidizing properties of higher valent manganese oxide layers that are formed upon ozonolysis of surface manganese sites.…”

Section: Introductionmentioning

confidence: 99%

Unusual stoichiometry control in the atomic layer deposition of manganese borate films from manganese bis(tris(pyrazolyl)borate) and ozone

Klesko

Bellow

Saly

et al. 2016

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

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Unusual stoichiometry control in the atomic layer deposition of manganese borate films from manganese bis(tris(pyrazolyl)borate) and ozone Klesko, Joseph P.; Bellow, James A.; Saly, Mark J.; Winter, Charles H.; Julin, Jaakko; Sajavaara, Timo Klesko, J. P., Bellow, J. A., Saly, M. J., Winter, C. H., Julin, J., & Sajavaara, T. (2016 C. The growth rate for the cobalt borate process was 0.39-0.42 Å /cycle at 325 C. X-ray diffraction of the as-deposited films indicated that they were amorphous. Atomic force microscopy of 35-36 nm thick manganese borate films grown within the 300-350 C ALD window showed root mean square surface roughnesses of 0.4-0.6 nm. Film stoichiometries were assessed by x-ray photoelectron spectroscopy and time of flight-elastic recoil detection analysis. The differing film stoichiometries obtained from the very similar precursors MnTp 2 and CoTp 2 are proposed to arise from the oxidizing ability of the intermediate high valent manganese oxide layers and lack thereof for cobalt.

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“…There have also been suggestions that the strongly alkaline nature of the stabilised showed high hydrolysis activity [62]. Hence, in theory, the Co-B catalysts should be able to be reused many times, as the reductive effect of the BH 4 -at the start of the reaction would reverse the oxidation that occurs towards the end of the reaction.…”

Section: Non-noble Metal Catalystsmentioning

confidence: 99%

Sodium borohydride production and utilisation for improved hydrogen storage

Muir¹

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Sodium borohydride (NaBH 4 ) has been the subject of extensive investigation as a potential hydrogen storage material. Its advantages include its ability to be stored as a stabilised aqueous solution and hydrolysed catalytically on demand, providing hydrogen safely, controllably, and at mild conditions. However, several drawbacks were identified by the US Department of Energy (DOE) in their "No-Go" recommendation in 2007; namely, the limitations on its gravimetric hydrogen storage capacity (GHSC) and its prohibitive manufacturing cost.This thesis aims to address some of the major issues associated with the use of NaBH 4 for hydrogen storage. Efforts have been spread across three key research areas, which were identified in a review of the recent literature: Synthesising an efficient, durable, and inexpensive catalyst for the hydrolysis of aqueous NaBH 4 solution  The design of a hydrogen storage system based on NaBH 4 which can overcome the GHSC constraints imposed by the solubility of its hydrolysis by-product, NaBO 2  The development of a novel recycling process for regenerating NaBH 4 from NaBO 2 , with the goal of reducing its production cost to within the DOE's target range of $2-4 per gallon of gasoline equivalent (gge) To achieve the first goal, a new electroless plating method was developed for preparing cobalt-boron (Co-B) catalysts supported on shaped substrates. This method involves mixing the plating solutions at low temperature (<5 o C), in contrast to previously employed methods, which are generally carried out at room temperature or higher. The new method requires only one plating step to achieve the desired catalyst loading, and has higher loading efficiency than processes requiring multiple plating steps, due to reduced catalyst wastage. The catalysts produced by this method show significantly higher NaBH 4 hydrolysis activity than those prepared by conventional methods, with a hydrogen generation rate over 24000 mL/min/g recorded at a temperature of 30 o C and a NaBH 4 concentration of 15 wt%. The improved activity of these catalysts was thought to be due to their increased boron content and nanosheet-like morphology, both of which are products of the low temperature preparation method.ii The stability of these catalysts was examined over several usage and deactivation cycles, which involved long-term exposure to alkaline solution. It was found that the deactivated catalysts were able to recover 80-90% of their initial activity even after 10 cycles, if operated at 40 o C or higher. Characterisation of the deactivated catalysts revealed that a layer of NaBO 2 had formed on the surface, blocking the catalytically active Co sites. The improved cyclic stability is most likely due to the dissolution of this layer at higher temperatures.A new reactor design for a NaBH 4 -based hydrogen storage system was developed, with the goal of overcoming the GHSC limitations encountered by conventional system designs. The new design is based on a fed-batch configuration in which solid NaBH 4 is added ...

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Cobalt borate catalysts for hydrogen production via hydrolysis of sodium borohydride

Cited by 73 publications

References 44 publications

Catalytic hydrolysis of sodium borohydride on Co catalysts

Catalytic hydrolysis of sodium borohydride on Co catalysts

Unusual stoichiometry control in the atomic layer deposition of manganese borate films from manganese bis(tris(pyrazolyl)borate) and ozone

Sodium borohydride production and utilisation for improved hydrogen storage

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