Exploring the Reactivity of Nickel Pincer Complexes in the Decomposition of Formic Acid to CO2/H2 and the Hydrogenation of NaHCO3 to HCOONa

Enthaler, Stephan; Brück, Andreas; Kammer, Anja; Junge, Henrik; Irran, Elisabeth; Gülak, Samet

doi:10.1002/cctc.201402716

Cited by 117 publications

(90 citation statements)

References 67 publications

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“…Besides, the turnover frequencies of Ti 3 C 2 T x -250, Pd/C, and Pt/C were calculated to be 960, 2679, and 4585 h −1 , respectively (Supplementary Table 5). Representative works on the dehydrogenation of HCOOH by homogeneous and heterogeneous non-noble-metal catalysts over past few years are listed in Supplementary Table 4 [15][16][17]20,22,24,[38][39][40][41][42][43][44] . Ti 3 C 2 T x -250 was among the best in heterogeneous catalysts.…”

Section: Resultsmentioning

confidence: 99%

Modulating oxygen coverage of Ti3C2Tx MXenes to boost catalytic activity for HCOOH dehydrogenation

et al. 2020

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As a promising hydrogen carrier, formic acid (HCOOH) is renewable, safe and nontoxic. Although noble-metal-based catalysts have exhibited excellent activity in HCOOH dehydrogenation, developing non-noble-metal heterogeneous catalysts with high efficiency remains a great challenge. Here, we modulate oxygen coverage on the surface of Ti 3 C 2 T x MXenes to boost the catalytic activity toward HCOOH dehydrogenation. Impressively, Ti 3 C 2 T x MXenes after treating with air at 250°C (Ti 3 C 2 T x-250) significantly increase the amount of surface oxygen atoms without the change of crystalline structure, exhibiting a mass activity of 365 mmol•g −1 •h −1 with 100% of selectivity for H 2 at 80°C, which is 2.2 and 2.0 times that of commercial Pd/C and Pt/C, respectively. Further mechanistic studies demonstrate that HCOO* is the intermediate in HCOOH dehydrogenation over Ti 3 C 2 T x MXenes with different coverages of surface oxygen atoms. Increasing the oxygen coverage on the surface of Ti 3 C 2 T x MXenes not only promotes the conversion from HCOO* to CO 2 * by lowering the energy barrier, but also weakens the adsorption energy of CO 2 and H 2 , thus accelerating the dehydrogenation of HCOOH.

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Section: Resultsmentioning

confidence: 99%

Modulating oxygen coverage of Ti3C2Tx MXenes to boost catalytic activity for HCOOH dehydrogenation

et al. 2020

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“…The dehydrogenation of FA to generate hydrogen has been extensively studied in the past few years. [2] Homogeneous catalysts based on ruthenium, [3] rhodium, [4] iridium, [5] iron, [6] and other complexes [7] have been widely investigated, and excellent results have been obtained. However,most of these catalytic systems for FA dehydrogenation require bases (e.g.,a mine) or additives (e.g.,L iBF 4 )i no rganic solvents.…”

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confidence: 99%

Unprecedentedly High Formic Acid Dehydrogenation Activity on an Iridium Complex with an N,N′‐Diimine Ligand in Water

Wang

Lü

et al. 2015

Chemistry A European J

140

119

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Hydrogen production from the dehydrogenation of formic acid (FA) is promising. Most of the current catalysts for FA dehydrogenation are effective only in the presence of bases or additives. We report here newly developed iridium complexes containing conjugated N,N'-diimine ligands for FA dehydrogenation in water without the addition of bases or additives. A turnover frequency (TOF) of 487 500 h(-1) with [Cp*Ir(L1)Cl]Cl (L1=2,2'-bi-2-imidazoline) at 90 °C and a turnover number (TON) of 2 400 000 with in situ prepared catalyst from [IrCp*Cl2 ]2 and 2,2'-bi-1,4,5,6-tetrahydropyrimidine (L2) at 80 °C were obtained, the highest values reported for FA dehydrogenation to date. A mechanistic study reveals that the formation of [Ir-H] intermediate species is the rate-determining step in the catalytic cycle.

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“…Many noble metal catalysts give outstanding performances for FA decomposition. Meanwhile, several complexes containing earth‐abundant metals have also been developed . In 2009, the catalytic performances of different nonprecious metal chlorides, such as Fe, Co, and Ni, are reported by Wills in FA/Et 3 N at 120 °C .…”

Section: The Advent and Development Of Homogeneous Fa Decomposition Rmentioning

confidence: 99%

“…Enthaler's group reported the first Ni‐based PCP pincer complex 20 for the FA decomposition to CO 2 and H 2 with the TON of up to 626 (Figure ) . However, the efficiency is not as good as those of others complexes .…”

Section: Catalysts With a Pincer‐type Ligandmentioning

confidence: 99%

An Update on Formic Acid Dehydrogenation by Homogeneous Catalysis

Guan

Pan

Zhang

et al. 2020

Chemistry An Asian Journal

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Formic acid (FA) has been extensively studied as one of the most promising hydrogen energy carriers today. The catalytic decarboxylation of FA ideally leads to the formation of CO2 and H2 that can be applied in fuel cells. A large number of transition‐metal based homogeneous catalysts with high activity and selectivity have been reported for the selective FA dehydrogentaion. In this review, we discussed the recent development of C,N/N,N‐ligand and pincer ligand‐based homogeneous catalysts for the FA dehydrogenation reaction. Some representative catalysts are further evaluated by the CON/COF assessment (catalyst on‐cost number)/(catalyst on‐cost frequency). Conclusive remarks are provided with future challenges and opportunities.

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Exploring the Reactivity of Nickel Pincer Complexes in the Decomposition of Formic Acid to CO₂/H₂ and the Hydrogenation of NaHCO₃ to HCOONa

Cited by 117 publications

References 67 publications

Modulating oxygen coverage of Ti3C2Tx MXenes to boost catalytic activity for HCOOH dehydrogenation

Modulating oxygen coverage of Ti3C2Tx MXenes to boost catalytic activity for HCOOH dehydrogenation

Unprecedentedly High Formic Acid Dehydrogenation Activity on an Iridium Complex with an N,N′‐Diimine Ligand in Water

An Update on Formic Acid Dehydrogenation by Homogeneous Catalysis

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