Preparation and characterization of Ni-M (M: Ru, Rh, Pd) nanoclusters as efficient catalysts for hydrogen evolution from ammonia borane methanolysis

Tunç, Nihat; Rakap, Murat

doi:10.1016/j.renene.2020.04.079

Cited by 47 publications

(17 citation statements)

References 57 publications

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“…145 The introduction of nickel for bimetallic alloying with these noble-metals was recently reported. 253 Hydroxyapatite[Ca 10 (PO 4 ) 6 (OH) 2 ]-supported RhNi@HAP, RuNi@HAP, and PdNi@HAP nanoparticles (average size ca 1.3 nm) were formed from HAP ion-exchange followed by in situ reduction by AB. Consistently, Rh 62 Ni 38 @HAP, Ru 80 Ni 20 @HAP, and Pd 80 Ni 20 @HAP nanocatalysts achieved the methanolysis of AB at 25 °C with TOF = 120, 59, and 25 min -1 , respectively.…”

Section: Alternative Solvolysis and Pyrolysismentioning

confidence: 99%

The Hydrogen‐Storage Challenge: Nanoparticles for Metal‐Catalyzed Ammonia Borane Dehydrogenation

Mboyi

Poinsot

Roger

et al. 2021

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Dihydrogen is one of the sustainable energy vectors envisioned for the future. However, the rapidly reversible and secure storage of large quantities of hydrogen is still a technological and scientific challenge. In this context, this review proposes a recent state-of-the-art on H 2 production capacities from the dehydrogenation reaction of ammonia borane (and selected related amine-boranes) as a safer solid-source of H 2 by hydrolysis (or solvolysis), according to the different developed nanoparticle-based catalysts. The review groups the results according to the transition metals constituting the catalyst according a special view to current cost/availability consideration. This includes the noble metals Rh, Pd, Pt, Ru, Ag, as well as transition metals such as Co, Ni, Cu, and Fe. For each element, the monometallic and polymetallic structures, isolated or supported, are presented and the performances described in terms of TOF and recyclability. The structure-property links are highlighted whenever possible. It appears from all these works that the mastery of the preparation of catalysts remains a crucial point; not only in terms of process but also in terms of mastery of the electronic structures of the elaborated nanomaterials. A particular effort of the scientific community remains to be made in this multidisciplinary field with major societal stakes.

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Section: Alternative Solvolysis and Pyrolysismentioning

confidence: 99%

The Hydrogen‐Storage Challenge: Nanoparticles for Metal‐Catalyzed Ammonia Borane Dehydrogenation

Mboyi

Poinsot

Roger

et al. 2021

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“…This region has also two other higher energy bands belong to the oxidized cobalt species due to the contact with the air oxygen [42] . In Figure 4d, Ni 2p region of the Ru 37 Ni 63 @NC nanoparticles are characterized by two bands standing for zerovalent nickel species and centered at 855.6 eV and 873.3 eV, respectively [43,44] . The other two higher energy bands (the one located around 882 eV strongly overlaps with the Ce 3d region) observed in this region of the Ru 37 Ni 63 @NC nanoparticles are due to the oxide formation on nanoparticle surfaces during sample handling [45] .…”

Section: Resultsmentioning

confidence: 89%

“…[42] In Figure 4d, Ni 2p region of the Ru 37 Ni 63 @NC nanoparticles are ChemistrySelect characterized by two bands standing for zerovalent nickel species and centered at 855.6 eV and 873.3 eV, respectively. [43,44] The other two higher energy bands (the one located around 882 eV strongly overlaps with the Ce 3d region) observed in this region of the Ru 37 Ni 63 @NC nanoparticles are due to the oxide formation on nanoparticle surfaces during sample handling. [45] Pd 3d region shown in Figure 4f has two evident bands centered at 335.3 eV for Pd 3d 5/2 and 340.6 eV for Pd 3d 3/ 2 as clear indications of zerovalent palladium species in the Ru 20 Pd 80 @NC nanoparticles.…”

Section: Synthesis Of Ethane 12-diamine Boranementioning

confidence: 99%

Nanoceria‐Supported Ru‐Based Nanoparticles as Highly Efficient Catalysts for Hydrolysis of Ethane 1,2‐Diamine Borane

Tunç

Rakap

2022

ChemistrySelect

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Here, the first ever preparation of some series of nanoceria‐supported Ru‐based nanoparticles with different compositions (RuxM100‐x@NC, M: Co, Ni, Pd) and their use as highly active catalysts to liberate hydrogen gas from hydrolysis of ethane 1,2‐diamine borane (EDAB) is reported. For the preparation of totally fifteen RuxM100‐x@NC nanoparticles with different compositions, the related metal cations are first supported on nanoceria surfaces by wet impregnation method in aqueous solution. Then, Ru3+‐M2+‐exchanged nanoceria samples are synchronously reduced during hydrolysis reaction of EDAB to form corresponding RuxM100x@NC nanoparticles meanwhile the formed nanoparticles catalyze the same reaction. RuxM100x@NC nanoparticles are identified by inductively coupled plasma‐optical emission spectroscopy (ICP‐OES), powder X‐ray diffraction (PXRD), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS), and BET surface area techniques. They provide quiet high catalytic activities in the hydrolysis reaction of EDAB. Among them, Ru20Pd80@NC nanoparticles are by far the best one up to date with a TOF value of 608.49 min−1 at 25 °C.

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“…23,29,30 The catalysis topic has been disproportionately investigated with a large number of possible catalysts reported so far. 34 Examples of recent catalysts are as follows: supported cobalt, [35][36][37] nickel, 38 bimetallics, 39,40 TiO 2, 41 metallurgic sludge, 42 polymer-based systems (eg, microgels), [43][44][45][46] treated microalgae, 47,48 and other natural materials like spent coffee. 49,50 With respect to the by-products like NaB(OCH 3 ) 4 , very few reports focused on their identification and their solid-state structure.…”

Section: Introductionmentioning

confidence: 99%

Closing the hydrogen cycle with the couple sodium borohydride‐methanol, via the formation of sodium tetramethoxyborate and sodium metaborate

et al. 2020

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Methanolysis of sodium borohydride (NaBH 4) is one of the methods efficient enough to release, on demand, the hydrogen stored in the hydride as well as in 4 equiv of methanol (CH 3 OH). It is generally reported that, in methanolysis, sodium tetramethoxyborate (NaB(OCH 3) 4) forms as single component of the spent fuel. It is, however, necessary to clearly investigate some critical aspects related to it. We first focused on the methanolysis reaction where NaBH 4 was reacted with 2, 4, 8, 16, or 32 equiv of CH 3 OH. With 2 equiv of CH 3 OH, the conversion of NaBH 4 is not complete. With 4 to 32 equiv of CH 3 OH, NaBH 4 is totally methanolized (conversion of 100%). The best conditions are those involving 4 equiv of CH 3 OH as they offer the highest effective gravimetric hydrogen storage capacity with 4.8 wt%, an attractive H 2 generation rate with 331 mL(H 2) min −1-a performance achieved without any catalyst-and the formation of NaB(OCH 3) 4 as single product as identified by X-ray diffraction, Fourier transform infrared spectroscopy, and nuclear magnetic resonance. We then focused on the transformation of this product NaB(OCH 3) 4 into sodium metaborate (NaBO 2), via the formation of sodium tetrahydroxyborate (NaB (OH) 4). NaB(OCH 3) 4 is easily transformed in water, by hydrolysis, at 80 C and for 90 minutes, into NaB(OH) 4 and 4 equiv of CH 3 OH. In doing so, the cycle with CH 3 OH is closed. Subsequently, NaB(OH) 4 is recovered and converted into NaBO 2 under heating at 500 C. This reaction liberates 4 equiv of H 2 O, which allows to close the cycle with water. Based on these achievements, we have finally proposed a triangular recycling scheme aiming at closing the cycle with the protic reactants of the aforementioned reactions. This scheme may be used as base for implementing a closed cycle with the couple NaBH 4-CH 3 OH.

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Preparation and characterization of Ni-M (M: Ru, Rh, Pd) nanoclusters as efficient catalysts for hydrogen evolution from ammonia borane methanolysis

Cited by 47 publications

References 57 publications

The Hydrogen‐Storage Challenge: Nanoparticles for Metal‐Catalyzed Ammonia Borane Dehydrogenation

The Hydrogen‐Storage Challenge: Nanoparticles for Metal‐Catalyzed Ammonia Borane Dehydrogenation

Nanoceria‐Supported Ru‐Based Nanoparticles as Highly Efficient Catalysts for Hydrolysis of Ethane 1,2‐Diamine Borane

Closing the hydrogen cycle with the couple sodium borohydride‐methanol, via the formation of sodium tetramethoxyborate and sodium metaborate

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