Catalytic interconversion between hydrogen and formic acid at ambient temperature and pressure

Maenaka, Yuta; Suenobu, Tomoyoshi; Fukuzumi, Shunichi

doi:10.1039/c2ee03315a

Cited by 200 publications

(170 citation statements)

References 64 publications

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“…However, the best results for hydrogen production reported to date have been obtained from the liquid phase decomposition of formic acid using homogeneous catalysts based on complexes of Rh (TOF=0.6 s -1 at 298 K) [38], Ru (TOF=1 s -1 at 323 K) [39,40], Fe (TOF=2.6 s -1 at 353 K) [24] or Ir (TOF=3.9 s -1 at 363 K) [41]. The highest activities obtained in our work, with a TOF value of 1 s -1 at 353 K and excellent hydrogen selectivity (>99.8%), are comparable to those for the decomposition of aqueous formic acid solutions using homogeneous catalysts.…”

Section: Discussionmentioning

confidence: 99%

Hydrogen production from formic acid vapour over a Pd/C catalyst promoted by potassium salts: Evidence for participation of buffer-like solution in the pores of the catalyst

Liu

Bulushev

Beloshapkin

et al. 2014

Applied Catalysis B: Environmental

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(D.A. Bulushev) 2 A B S T R A C T Doping a 1 wt.% Pd/C catalyst with alkali metal carbonates has a very significant promotional effect on its activity in hydrogen production from the decomposition of formic acid vapour (2 vol.%, 1 bar), potassium and caesium carbonates giving the largest effects. The K carbonate species present on the fresh catalysts react with formic acid to form formate ions, these being dissolved in a formic acid/water solution condensed in the pores of the support. The steadystate activities of the samples containing formate ions were 1-2 orders of magnitude greater than those of the unpromoted Pd/C and CO content was lower than 30 ppm. The activation energies for the reaction increased with doping from 66 to 88-99 kJ mol -1 , relatively independent of the cation of the dopant. Similar but lesser effects were found with unsupported Pd nanocrystals doped with K carbonate. The rate-determining step for the promoted samples appears to be the decomposition of formate ions on the Pd surface.

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Section: Discussionmentioning

confidence: 99%

Hydrogen production from formic acid vapour over a Pd/C catalyst promoted by potassium salts: Evidence for participation of buffer-like solution in the pores of the catalyst

Liu

Bulushev

Beloshapkin

et al. 2014

Applied Catalysis B: Environmental

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“…[37] Catalysts 3, 6, and 7 possessing OH substituents on ligands showed highly activity (Entries 13-15, TOF; 27-66 h −1 ). Until now, except for our catalysts, only Fukuzumi's catalyst has achieved to progress the reaction under the conditions, but its catalytic activity was very low with TOF of 6.8 h −1 .…”

Section: Wwwadvancedsciencenewscommentioning

confidence: 99%

Development of Effective Catalysts for Hydrogen Storage Technology Using Formic Acid

Onishi

Iguchi

Yang

et al. 2018

Advanced Energy Materials

128

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We are engaged in research and development to reduce CO 2 emissions. Longterm increase of CO 2 concentration in the atmosphere has a great influence on climate change. [1] Therefore, developing technologies aiming to reduce CO 2 emissions and to overcome the present society depending on fossil fuels as primary energy. Additionally, transition of fossil fuels into renewable energies is also important for realizing future sustainable society. [2] The most suitable material for this goal is considered to be hydrogen, because its combustion emits only water as a byproduct. In addition, hydrogen possesses almost three times as much energy as natural gases, and can supply electric power very efficiently for fuel cells without releasing greenhouse gases and air pollutants. [3] However, hydrogen also has serious drawbacks for practical applications. Most serious problem is that, hydrogen forms as a gas at ambient conditions with very low density (0.0899 kg m −3 at 0 °C, 0.10 MPa) over ten times lower than air (1.293 kg m −3 at 0 °C, 0.10 MPa). As a result, it becomes difficult to store and transport hydrogen safely. Developing safe and efficient hydrogen storage materials is one of the most difficult challenges for the transformation from the fossil fuel-based economy to hydrogen-based one as a long-term solution for a safe energy future.Hydrogen has attracted considerable attention as an energy source, and various attempts to develop suitable methods for hydrogen generation are made at the National Institute of Advanced Industrial Science and Technology. In this paper, the authors introduce their recent strategies to store hydrogen using formic acid (FA) as a hydrogen carrier. FA, which is believed to be one of the most promising liquid organic hydrogen carriers, can provide a viable method for safe hydrogen transportation. In order to optimize the performance of hydrogen storage with FA, the authors have investigated both homogeneous and heterogeneous catalysts. For example, Ir catalysts anchoring N^N-bidentate ligands show high catalytic activity for both the reactions of FA synthesis and hydrogen generation from FA. Ultrafine Pd-based nanoparticles are also immobilized on various supports, which show excellent catalytic performance for FA dehydrogenation under mild conditions. The authors also develop both homogeneous and heterogeneous catalysts to generate high-pressure gases (H 2 and CO 2 ) over 120 and 35 MPa, respectively,

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“…[26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41] CO 2 fixation by hydrogen has conjointly been created doable by exploitation of homogeneous catalysts under normal pressure of H 2 and carbon dioxide and at room temperature as well. [42][43][44][45][46] The step of water oxidation is the bottleneck of artificial photosynthesis because it needs the removal of four protons and four electrons from the catalytic site. In nature, the compound that achieves water splitting in the photosynthesis process is the oxygenevolving complex (OEC), which exists in photosystem II, is known to be manganese-oxo-calcium cluster.…”

Section: Introductionmentioning

confidence: 99%

Earth-abundant metal complexes as catalysts for water oxidation; is it homogeneous or heterogeneous?

Asraf

Younus

Yusubov

et al. 2015

Catal. Sci. Technol.

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MINIREVIEW This journal isRecent developments in the oxidation of water to dioxygen using metal complexes as catalysts or precatalysts are represented at the side of the conversion of homogeneous catalysts into nanoparticles or heterogeneous one during the oxidation reaction of water. Homogeneous catalysts are advantageous within the careful design and elucidation of the mechanisms for the catalytic water oxidation. In distinction, the uses of heterogeneous catalysts in water oxidation are advantageous for sensible applications as a result of their robust catalytic activity. Though detailed studies on homogeneous and heterogeneous water oxidation reactions are performed rather severally, the connection of homogeneous catalysts with heterogeneous one is changing into an additional requirement for the event of economic attractive water oxidation catalysts (WOCs). This minireview focuses on the aspects if the particular catalysts for the oxidation of water are homogeneous or heterogeneous.

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Catalytic interconversion between hydrogen and formic acid at ambient temperature and pressure

Cited by 200 publications

References 64 publications

Hydrogen production from formic acid vapour over a Pd/C catalyst promoted by potassium salts: Evidence for participation of buffer-like solution in the pores of the catalyst

Hydrogen production from formic acid vapour over a Pd/C catalyst promoted by potassium salts: Evidence for participation of buffer-like solution in the pores of the catalyst

Development of Effective Catalysts for Hydrogen Storage Technology Using Formic Acid

Earth-abundant metal complexes as catalysts for water oxidation; is it homogeneous or heterogeneous?

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