Fundamental Mechanisms of Reversible Dehydrogenation of Formate on N-Doped Graphene-Supported Pd Nanoparticles

Shin, Dongyun; Kim, Min-Su; Kwon, Jeong An; Shin, Yeon-Jeong; Yoon, Chang Won; Lim, Dong‐Hee

doi:10.1021/acs.jpcc.8b07002

Cited by 34 publications

(35 citation statements)

References 61 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…644 Another study has also shown that the metal support interaction can be used to shift the d-band center of Pd in N-doped carbon, the smallest d-band center resulting in the lowest energy barrier for formic acid dehydrogenation. 645 Electro-deficient metal NP were also demonstrated to be superior in the case of dehydrogenation of ammonia borane on Pt/CNT catalysts. 646 It was proposed that on oxidized CNT (large amount of oxygen surface group) the charge transfer occurs from the CNT to Pt, whereas on defective CNT (defects and small amount of oxygen surface group), the charge transfer occurs from the Pt to the support.…”

Section: Ag8/n-gmentioning

confidence: 99%

A Theory/Experience Description of Support Effects in Carbon-Supported Catalysts

2019

View full text Add to dashboard Cite

Fermi level in vii) are shown in purple in ii)-vi) with an iso-value of ±0.003 a.u. Reprinted with permission from ref 57 . Copyright 2014 from the Royal Society of Chemistry; b) Molecular model of a corannulene-like element functionalized with three carboxylic groups from two different perspectives in the cpk representation (on the left). The final structure (190 elements in a cubic cell of 60 Å in size) obtained from random packing of the individual elements (on the right). Cyan: carbon, red: oxygen, white: hydrogen. Reprinted with permission from ref 59 Copyright 2017 from Elsevier; c) Side-views of Ru13 adsorbed on Gr-DV-2COOH site before (on left panel) and after a proton jump (right panel). C atoms are in black, O in red, H in with white and Ru in mocha. Reprinted with permission from ref 60 Copyright 2014 from Elsevier; and d) Spin-density projection in µB/a.u. 2 on the graphene plane around i) the hydrogen chemisorption defect (∆) and ii) the vacancy defect in the a sublattice. Carbon atoms corresponding to the a sublattice (o) and to the b sublattice (•) are distinguished. Simulated STM images of the defects are shown in iii) and iv), respectively. Reprinted with permission from ref 61 .

show abstract

Section: Ag8/n-gmentioning

confidence: 99%

A Theory/Experience Description of Support Effects in Carbon-Supported Catalysts

2019

View full text Add to dashboard Cite

show abstract

“…Yoon and co-workers reported density functional theory (DFT)-based mechanistic details of these reversible reactions on a Pd-based catalyst and proposed the key points for improving the efficiency of the reaction. [99] Figure 20 shows the mechanism of reversible dehydrogenation and hydrogenation of HCOO À on Ndoped graphene supported Pd nanocatalyst. The DFT modeling is aimed at identifying the factors responsible for efficiency of the reaction.…”

Section: Mechanistic Investigation Of Reversible Formate-bicarbonate mentioning

confidence: 99%

“…Blue and red arrows represent HCOO À dehydrogenation and HCO 3 À hydrogenation, respectively. Reproduced with permission from Ref [99]…”

mentioning

confidence: 99%

Formate‐Bicarbonate Cycle as a Vehicle for Hydrogen and Energy Storage

Bahuguna

Sasson

2020

ChemSusChem

View full text Add to dashboard Cite

In recent years, hydrogen has been considered a promising energy carrier for a sustainable energy economy in the future. An easy solution for the safer storage of hydrogen is challenging and efficient methods are still being explored in this direction. Despite having some progress in this area, no cost‐effective and easily applicable solutions that fulfill the requirements of industry are yet to be claimed. Currently, the storage of hydrogen is largely limited to high‐pressure compression and liquefaction or in the form of metal hydrides. Formic acid is a good source of hydrogen that also generates CO2 along with hydrogen on decomposition. Moreover, the hydrogenation of CO2 is thermodynamically unfavorable and requires high energy input. Alkali metal formates are alternative mild and noncorrosive sources of hydrogen. On decomposition, these metal formates release hydrogen and generate bicarbonates. The generated bicarbonates can be catalytically charged back to alkali formates under optimized hydrogen pressure. Hence, the formate‐bicarbonate‐based systems being carbon neutral at ambient condition has certain advantages over formic acid. The formate‐bicarbonate cycle can be considered as a vehicle for hydrogen and energy storage. The whole process is carbon‐neutral, reversible, and sustainable. This Review emphasizes the various catalytic systems employed for reversible formate‐bicarbonate conversion. Moreover, a mechanistic investigation, the effect of temperature, pH, kinetics of reversible formate‐bicarbonate conversion, and new insights in the field are also discussed in detail.

show abstract

“…These changes could take place on the same time scale as the growth of the particles and be closely connected. In such case, there might be significant electronic effects, which affect the binding energy between catalyst, reactants, and products, and inhibit facile product release [43].…”

Section: Co + H 2 O ⇋ Co 2 + Hmentioning

confidence: 99%

Research Requirements to Move the Bar forward Using Aqueous Formate Salts as H2 Carriers for Energy Storage Applications

Grubel¹,

Su²,

Kothandaraman³

et al. 2020

JEPT

View full text Add to dashboard Cite

In this perspective on hydrogen carriers, we focus on the needs for the development of robust active catalysts for the release of H2 from aqueous formate solutions, which are non-flammable, non-toxic, thermally stable, and readily available at large scales at reasonable cost. Formate salts can be stockpiled in the solid state or dissolved in water for long term storage and transport using existing infrastructure. Furthermore, formate salts are readily regenerated at moderate pressures using the same catalyst as for the H2 release. There have been several studies focused on increasing the activity of catalysts to release H2 at moderate temperatures, i.e., < 80 °C, below the operating temperature of a proton exchange membrane (PEM) fuel cell. One significant challenge to enable the use of aqueous formate salts as hydrogen carriers is the deactivation of the catalyst under operating conditions. In this work we provide a review of the most efficient heterogeneous catalysts that have been described in the literature, their proposed modes of deactivation, and the strategies reported to reactivate them. We discuss potential pathways that may lead to deactivation and strategies to mitigate it in a variety of H2 carrier applications. We also provide an example of a potential use case employing formate salts solutions using a fixed bed reactor for seasonal storage of energy for a microgrid application.

show abstract

Fundamental Mechanisms of Reversible Dehydrogenation of Formate on N-Doped Graphene-Supported Pd Nanoparticles

Cited by 34 publications

References 61 publications

A Theory/Experience Description of Support Effects in Carbon-Supported Catalysts

A Theory/Experience Description of Support Effects in Carbon-Supported Catalysts

Formate‐Bicarbonate Cycle as a Vehicle for Hydrogen and Energy Storage

Research Requirements to Move the Bar forward Using Aqueous Formate Salts as H2 Carriers for Energy Storage Applications

Contact Info

Product

Resources

About