Efficient pH-gradient-enabled microscale bipolar interfaces in direct borohydride fuel cells

Wang, Zhongyang; Parrondo, Javier; He, Cheng; Sankarasubramanian, Shrihari; Ramani, Vijay

doi:10.1038/s41560-019-0330-5

Cited by 69 publications

(108 citation statements)

References 58 publications

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“…[140] Moreover, Nguyen and co-workers argued that the values of a T1 diagnostic (from the CCSD(T)) are small, indicating that boron-hydrogen compounds do not possess significant multireference character; thus, suggesting the heats of formation of boron-hydrogen compounds need to be remeasured. [107] Inspection of Table 2 and Figure 3 shows that the highest heat of formation (positive ΔH o f , the amount of energy or heat absorbed during the formation of the substance) is that for B 5 H 2À 5 (8) and the lowest (negative ΔH o f , the amount of energy or heat released during the formation of the substance) is that for B 12 H 2À 12 (21). The heats of formation values of closoboranes, from penta-closoborane (B 5 H 2À 5 (8)) to dodeca-closoborane (B 12 H 2À 12 (21)) show a gradual decrease from + 109.91 to À 102.43 kcal/mol.…”

Section: Heats (Enthalpies) Of Formationmentioning

confidence: 99%

“…Boron‐hydrogen compounds are receiving a lot of attention due to their diverse physical and chemical properties, which can be useful for various technological applications ranging from hydrogen storage, fuel cells to high conducting materials even at room temperature as well as for applications in medicinal chemistry . Boranes and carboranes are recently targeted because of their potential to form

BH \cdot \cdot \cdot π

interactions with the π ‐face of an arene .…”

Section: Introductionmentioning

confidence: 99%

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Quantitative Assessment of B−B−B, B−H_b−B, and B−H_t Bonds: From BH₃ to B₁₂H₁₂²⁻

et al. 2019

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We report the thermodynamic stabilities and the intrinsic strengths of three‐center‐two‐electron B−B−B and B−Hb−B bonds (Hb : bridging hydrogen), and two‐center‐two‐electron B−Ht bonds (Ht : terminal hydrogen) which can be served as a new, effective tool to determine the decisive role of the intermediates of hydrogenation/dehydrogenation reactions of borohydride. The calculated heats of formation were obtained with the G4 composite method and the intrinsic strengths of B−B−B, B−Hb−B, and B−Ht bonds were derived from local stretching force constants obtained at the B3LYP‐D2/cc‐pVTZ level of theory for 21 boron‐hydrogen compounds, including 19 intermediates. The Quantum Theory of Atoms in Molecules (QTAIM) was used to deepen the inside into the nature of B−B−B, B−Hb−B, and B−Ht bonds. We found that all of the experimentally identified intermediates hindering the reversibility of the decomposition reactions are thermodynamically stable and possess strong B−B−B, B−Hb−B, and B−Ht bonds. This proves that thermodynamic data and intrinsic B−B−B, B−Hb−B, and B−Ht bond strengths form a new, effective tool to characterize new (potential) intermediates and to predict their role for the reversibility of the hydrogenation/dehydrogenation reactions.

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Section: Heats (Enthalpies) Of Formationmentioning

confidence: 99%

BH \cdot \cdot \cdot π

interactions with the π ‐face of an arene .…”

Section: Introductionmentioning

confidence: 99%

Quantitative Assessment of B−B−B, B−H_b−B, and B−H_t Bonds: From BH₃ to B₁₂H₁₂²⁻

et al. 2019

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“…To date, cation-exchange membranes are more mature than their anion-exchange counterparts, and bipolar membranes are at an early stage of development. All types of ion-exchange membranes can be used in a DBFC (see for example [24,25]), and, whatever the nature of the membrane/separator, there are drawbacks to their utilization. For a cation-exchange membrane, during DBFC operation, the Na + cation shall migrate to the cathode, where it 4 will combine with the OHspecies formed in the alkaline oxygen reduction reaction (ORR), thereby displacing the NaOH from the anolyte to the cathode side.…”

Section: Introductionmentioning

confidence: 99%

Oxygen Reduction Reaction on Metal and Nitrogen–Doped Carbon Electrocatalysts in the Presence of Sodium Borohydride

et al. 2020

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Metal and nitrogen-doped carbons electrocatalysts (M-N-C, where M is Fe or Co) are investigated for the oxygen reduction reaction (ORR) in alkaline conditions in the presence of borohydride ions (BH4-). The electrochemical properties of the Fe-N-C and CoN -C catalysts were investigated by cyclic voltammetry and rotating disk electrode 2 techniques: their ORR electrocatalytic activity was bridged to their physico-chemical properties, mainly type of metallic center (Fe vs. Co), structure (atomic dispersion vs. nanoparticles) and BET surface area. It is found that Fe-N-C catalysts have the best performances for the ORR electrocatalysis, even in presence of BH4anions. The atomically-dispersed Fe-and Co-containing electrocatalysts reach better BH4-tolerance than their counterparts baring nanoparticles. For the atomically dispersed Fe-N-C electrocatalysts, the lowest BET surface area material generates a slight advantage of ORR mass activity and a poor (and desired) activity for borohydride oxidation reaction (BOR).

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“…Metal hydroborates and their derivatives are attracting a lot of interest in the field of energy applications . The ion BH 4 − is very light and contains a high mass fraction of hydrogen, which makes it attractive as part of hydrogen storage systems for mobile applications .…”

Section: Introductionmentioning

confidence: 99%

“…Further, the closoborates B 10 H 10 2− , B 12 H 12 2− and related species have attracted some interest in recent years for solid state battery applications. These large and rather rigid ions, combined with small lithium or sodium cations, form crystals which present at high temperatures highly ionic conducting phases . In contrast to the reactive BH 4 − , these closoborates present high chemical stability, in addition to a large electrochemical window, which makes these compounds promising candidates for solid state battery applications.…”

Section: Introductionmentioning

confidence: 99%

Estimation of Thermodynamic Properties of Metal Hydroborates

Hagemann

2019

ChemistrySelect

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Metal hydroborates from M(BH 4 ) n to M x (B 12 H 12 ) y currently attract a strong interest for potential applications in the field of hydrogen storage and more recently as solid ionic conductors. While thermodynamic data for the alkali borohydrides (MBH 4 ) are well known, experimental data for other compounds are cruelly lacking. Using a combination of theoretical (DFT) and experimental data, we calculate the lattice enthalpy for a series of borohydrides. The comparison with literature data show that these lattice enthalpies are very similar to those of the corresponding metal bromides. This similarity is at the origin of a good correlation between the formation enthalpy of bromides and borohydrides which is then used to estimate the previously unknown formation enthalpy of M II (BH 4 ) 2 (M II = divalent cation) and Ln(BH 4 ) 3 (Ln = lanthanide). The Gibbs free energy of formation of M 2 (B 12 H 12 ) (M = alkali metal) is also estimated.[a] Prof.

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Efficient pH-gradient-enabled microscale bipolar interfaces in direct borohydride fuel cells

Cited by 69 publications

References 58 publications

Quantitative Assessment of B−B−B, B−H_b−B, and B−H_t Bonds: From BH₃ to B₁₂H₁₂²⁻

Quantitative Assessment of B−B−B, B−H_b−B, and B−H_t Bonds: From BH₃ to B₁₂H₁₂²⁻

Oxygen Reduction Reaction on Metal and Nitrogen–Doped Carbon Electrocatalysts in the Presence of Sodium Borohydride

Estimation of Thermodynamic Properties of Metal Hydroborates

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Efficient pH-gradient-enabled microscale bipolar interfaces in direct borohydride fuel cells

Cited by 69 publications

References 58 publications

Quantitative Assessment of B−B−B, B−Hb−B, and B−Ht Bonds: From BH3 to B12H122−

Quantitative Assessment of B−B−B, B−Hb−B, and B−Ht Bonds: From BH3 to B12H122−

Oxygen Reduction Reaction on Metal and Nitrogen–Doped Carbon Electrocatalysts in the Presence of Sodium Borohydride

Estimation of Thermodynamic Properties of Metal Hydroborates

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Quantitative Assessment of B−B−B, B−H_b−B, and B−H_t Bonds: From BH₃ to B₁₂H₁₂²⁻

Quantitative Assessment of B−B−B, B−H_b−B, and B−H_t Bonds: From BH₃ to B₁₂H₁₂²⁻