Formic Acid Dehydrogenation for Hydrogen Production Promoted by Grubbs and Hoveyda‐Grubbs Catalysts^†

Abstract

on the occasion of her 10th founding anniversary.

New Tricks for an Old Dog: Grubbs Catalysts Enable Efficient Hydrogen Production from Aqueous-Phase Methanol Reforming

“…The presence of unreacted formate and a trace amount of carbonate in the product mixture was further confirmed by 1 H and 13 C NMR (Figures S2–S4), while GC analysis indicated a negligible amount of CO 2 in the gaseous product. The presence of formate can be rationalized by the pH-dependent reactivity of formic acid for dehydrogenation observed by us and other researchers; we found that there is an optimal pH for the effective dehydrogenation of HCOOH. Moreover, additional experiments were conducted to examine the quantitative relationship between the amount of H 2 produced and the amount of HCOOK present (Table S2).…”

“…Hydrogen gas (H 2 ) is one of the most promising green and sustainable energy carriers and can be directly converted into electricity by fuel-cell technology . However, practical applications are hampered by its low volumetric energy density and highly explosive nature, which add to the cost of storage, transport, and handling. , Chemical storage of hydrogen in liquid organic hydrogen carriers (LOHCs) offers an attractive alternative: hydrogen gas can be generated on demand upon chemical reaction of a carrier molecule that is otherwise stable and can be easily handled and transported. − Methanol is one such carrier of interest due to its high hydrogen content (12.6 wt % or 99.8 g L –1 ) and ready accessibility from biomass or industrial sources . In the presence of a catalyst, H 2 can be “liberated” by way of a three-step reaction.…”

Hydrogen production via the aqueous-phase reforming of methanol catalyzed by Ru(ii) complexes of PNNP ligands

“…High-resolution electrospray ionization mass spectrometric (HRESI-MS) analysis of the reaction mixture with 2 as the catalyst was conducted to identify any species involved in the process. 33,77,78 The reaction mixture of entry 2 in Table 1 provides plentiful information on the nature of the Ru-containing species, depicting excellent matches between the experimental and simulated data with a deviation of <5 ppm (Fig. 6a over the course of the reaction (Fig.…”

“…A mixture of the dichloro-( p-cymene)ruthenium (II) dimer (0.49 g, 0.8 mmol) and L1 (1.03 g, 1.6 mmol) in toluene(20 mL) was heated under reflux for 12 h under an argon atmosphere and then cooled to room temperature. The crude solid product was obtained by removing the solvent under vacuum, followed by purification by alumina column chromatography using dichloromethane as the eluent and then recrystallized from dichloromethane/n-hexane (0 78. g, 54% yield).…”

Cyclic Amide-Anchored NHC-Based Cp*Ir Catalysts for Bidirectional Hydrogenation–Dehydrogenation with CO2/HCO2H Couple

“…With these couples, not only an effective carbon-neutral H 2 -based fuel system but also the carbon capture and utilization (CCU) protocol can be implemented at a time. − Obviously, to materialize such systems, among other factors, developing efficient catalysts for bidirectional CO 2 (or HCO 3 – ) hydrogenation and HCO 2 H (or HCO 2 – ) dehydrogenation is equally important. In the domain of homogeneous transition metal-based catalysis, although a great advancement has already been achieved for the individual hydrogenation − and dehydrogenation − reactions with two different catalysts, there are only a limited number of reports in the literature describing both the processes using a single catalyst. − Among these, some catalysts are relatively more active in hydrogenation than dehydrogenation, , while some others are the opposite. ,,, Single bidirectional transition metal catalysts, which are highly efficient in both hydrogenation and dehydrogenation, are so far designed with phosphine-based (PNP pincer) or N , N -donor-based ligands (Figure B).…”