Hydrogenation of aqueous mixtures of calcium carbonate and carbon dioxide using a water-soluble rhodium(I)–tertiary phosphine complex catalyst

Jószai, István; Joó, Ferenc

doi:10.1016/j.molcata.2004.08.045

Cited by 58 publications

(26 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[91] Over 10 years later, TOFs of around 30 h À1 were reported based on rhodium phosphine catalysts at room temperature and 70 8C. [86,87] With the dinuclear complex [Ru 2 (m-CO)(CO) 4 (m-dppm) 2 ] as a catalyst for the decomposition of formic acid without a base, a TOF up to 500 h À1 after 20 min was observed. [94] With a rhodium bipyridine catalyst, a TOF of 238 h À1 was achieved at 40 8C.…”

Section: Homogeneous Catalytic Decompositionmentioning

confidence: 99%

Liquid‐Phase Chemical Hydrogen Storage: Catalytic Hydrogen Generation under Ambient Conditions

et al. 2010

View full text Add to dashboard Cite

There is a demand for a sufficient and sustainable energy supply. Hence, the search for applicable hydrogen storage materials is extremely important owing to the diversified merits of hydrogen energy. Lithium and sodium borohydride, ammonia borane, hydrazine, and formic acid have been extensively investigated as promising hydrogen storage materials based on their relatively high hydrogen content. Significant advances, such as hydrogen generation temperatures and reaction kinetics, have been made in the catalytic hydrolysis of aqueous lithium and sodium borohydride and ammonia borane as well as in the catalytic decomposition of hydrous hydrazine and formic acid. In this Minireview we briefly survey the research progresses in catalytic hydrogen generation from these liquid-phase chemical hydrogen storage materials.

show abstract

Section: Homogeneous Catalytic Decompositionmentioning

confidence: 99%

Liquid‐Phase Chemical Hydrogen Storage: Catalytic Hydrogen Generation under Ambient Conditions

et al. 2010

View full text Add to dashboard Cite

show abstract

“…[13] Formic acid is prepared commercially from carbon monoxide and also as by-product in the synthesis of other chemicals. [14] Numerous studies have demonstrated formic acid production from carbon dioxide, [15] either electrochemically [16] or in aqueous [10,17] or supercritical phases, [18] which require bicarbonate instead of CO 2 or addition of a base. Hence, a "green" CO 2 cycle could be achieved by separation of the CO 2 generated [19] and its conversion into formic acid using hydrogen from a stationary source (Scheme 1).…”

mentioning

confidence: 99%

A Viable Hydrogen‐Storage System Based On Selective Formic Acid Decomposition with a Ruthenium Catalyst

2008

View full text Add to dashboard Cite

Hydrogen represents an important alternative energy feedstock for both environmental and economic reasons, and when combined with fuel-cell technology, very efficient energy conversion can be achieved.[1] Although the advantages of hydrogen over fossil fuels are numerous, the actual use of hydrogen as a transportation fuel is limited mainly because of storage and delivery problems. Conventional hydrogen-storage methods, such as high-pressure gas containers and cryogenic liquid/gas containers, have weight and safety issues.[2] Consequently, a great deal of research is being undertaken to develop new materials, such as metal hydrides [2,3] and carbon nanostructures, [4] that store hydrogen efficiently, although no entirely satisfactory options have been found so far. Formic acid containing 4.4 wt % of hydrogen, as well as its conjugate base, formate salt, are well known sources of hydrogen [5][6][7] and have previously been reported as potential hydrogen-storage material.[8] Formic acid has the advantage over other substrates that only gaseous products are formed (H 2 /CO 2 ), hence preventing the accumulation of by-products, which is a limitation for mobile applications. However, until now potential applications have been limited by catalyst regeneration requirements, by harsh reaction conditions, and by poor selectivity. We present herein an efficient, completely selective, and robust system for hydrogen production from formic acid using water-soluble homogeneous catalysts. [9] Decomposition of formic acid was carried out in aqueous solution using hydrophilic ruthenium-based catalysts, generated from the highly water-soluble ligand meta-trisulfonated triphenylphosphine (TPPTS) with either [Ru(H 2 O) 6 ] 2+ or, more conveniently, commercially available RuCl 3 .The catalysts were activated prior to use by reaction with sodium formate and formic acid and the catalytic decomposition of formic acid performed under a wide range of pressures and temperatures. The generated H 2 /CO 2 pressure was typically between 1 and 220 bar, but no inhibition of catalytic activity was observed up to a pressure of 750 bar (see the Supporting Information for details). The rate of formic acid decomposition increased with temperature, and at all temperatures a conversion of 90-95 % can be achieved (Figure 1). The total conversion does not reach 100 % because the formate salt added for the activation of the catalyst is not converted; however, all the formic acid is consumed.[10] In addition, the catalyst was stable up to 170 8C and remained active after one year in solution.The thermal decomposition of formic acid into CO and H 2 O, which depends on the temperature and the formic acid concentration, becomes nonnegligible at elevated temperatures. [11] No traces of CO, which is known to poison some fuel cells, [12] could be detected by FTIR spectroscopy (detection limit of 3 ppm) in a sample of gases generated by using this catalyst system at 100 8C (see the Supporting Information), because of the rapidity of the reaction and, hence, the ...

show abstract

“…[4a] and Jóo et al [14] reached turnover frequencies of approximately 30 h À1 at room temperature and 70 8C, respectively. Himeda et al obtained TOFs of 238 h À1 with rhodium bipyridine catalysts at 40 8C.…”

mentioning

confidence: 99%

Controlled Generation of Hydrogen from Formic Acid Amine Adducts at Room Temperature and Application in H₂/O₂ Fuel Cells

et al. 2008

View full text Add to dashboard Cite

show abstract

Hydrogenation of aqueous mixtures of calcium carbonate and carbon dioxide using a water-soluble rhodium(I)–tertiary phosphine complex catalyst

Cited by 58 publications

References 30 publications

Liquid‐Phase Chemical Hydrogen Storage: Catalytic Hydrogen Generation under Ambient Conditions

Liquid‐Phase Chemical Hydrogen Storage: Catalytic Hydrogen Generation under Ambient Conditions

A Viable Hydrogen‐Storage System Based On Selective Formic Acid Decomposition with a Ruthenium Catalyst

Controlled Generation of Hydrogen from Formic Acid Amine Adducts at Room Temperature and Application in H₂/O₂ Fuel Cells

Contact Info

Product

Resources

About

Hydrogenation of aqueous mixtures of calcium carbonate and carbon dioxide using a water-soluble rhodium(I)–tertiary phosphine complex catalyst

Cited by 58 publications

References 30 publications

Liquid‐Phase Chemical Hydrogen Storage: Catalytic Hydrogen Generation under Ambient Conditions

Liquid‐Phase Chemical Hydrogen Storage: Catalytic Hydrogen Generation under Ambient Conditions

A Viable Hydrogen‐Storage System Based On Selective Formic Acid Decomposition with a Ruthenium Catalyst

Controlled Generation of Hydrogen from Formic Acid Amine Adducts at Room Temperature and Application in H2/O2 Fuel Cells

Contact Info

Product

Resources

About

Controlled Generation of Hydrogen from Formic Acid Amine Adducts at Room Temperature and Application in H₂/O₂ Fuel Cells