Photo-hydrogen-evolving molecular devices driving visible-light-induced water
reduction into molecular hydrogen: structure–activity relationship and reaction mechanism
This article describes the structure–activity relationship and reaction mechanism of photo-hydrogen-evolving molecular devices made up of Ru(II) sensitizers and Pt(II) molecular catalysts.
Activation of dihydrogen by non-metal systems
This article reviews advances in the metal-free activation of hydrogen and the utilization of these and related systems in catalytic hydrogenations.
Transition metal catalysed ammonia-
borane dehydrogenation in ionic liquids
Significant advantages result from combining the disparate hydrogen release pathways for ammonia-borane (AB) dehydrogenation using ionic liquids (ILs) and transition metal catalysts. With the RuCl2(PMe3)4 catalyst precursor, AB dehydrogenation selectivity and extent are maximized in an IL with the moderately coordinating ethylsulfate anion.
Transition metal catalysed
dehydrogenation of amine- borane fuel blends
Mixtures containing ammonia-borane and sec-butylamine-borane remain liquid throughout the hydrogen release process that affords tri(N-sec-butyl)borazine and polyborazylene.
nanotube network: a novel 3-D nanostructured material with enhanced hydrogen storage capacity
Porous nanotube networks are a novel family of ‘carbon superstructures’ with superior structural characteristics and many potential applications.
Heterobimetallic rhodium–gold halide and
Thermal and photochemical reactions relevant to photocatalytic hydrogen production have been investigated on rhodium–gold heterobimetallic constructs.
Facile metal free regioselective transfer
hydrogenation of polarized olefins with ammonia borane
Transfer hydrogenation of polarized olefins with ammonia borane was achieved at room temperature proceeding stepwise with a unique hydroboration intermediate.
Towards a structure-performance relationship for hydrogen storage in Ti-doped NaAlH4 nanoparticles
By adding a Ti catalyst to nanosized NaAlH4 (<20 nm) hydrogen desorption rates are enhanced. Adding the Ti catalyst before the alanate resulted in a superior material.
Photocatalytic H2 evolution from neutral
water with a molecular cobalt catalyst on a dye-sensitised TiO2 nanoparticle
A cobaloxime catalyst evolves H2 photocatalytically when attached on dye-sensitised TiO2.
catalyst precursor K2TiF6 with remarkable synergetic effects of K, Ti and F together on reversible hydrogen storage of NaAlH4
A synergetic effect of K, Ti and F together on improving the reversible hydrogen storage properties of NaAlH4 is found by intruding K2TiF6 as catalyst precursor.
storage properties and neutron scattering studies of Mg2(dobdc)—a metal–organic framework with open Mg2+
The hydrogen storage properties of Mg2(dobdc) are probed by adsorption experiments, infrared spectroscopy, and neutron scattering techniques, demonstrating that the open coordination sites are of benefit for high-density storage."
dehydrogenation of magnesium borohydride to magnesium triborane in the solid state under moderate conditions
The solid state dehydrogenation of Mg(BH4)2 to Mg(B3H8)2 has been shown to be reversible under the conditions of moderate temperature and pressure that preclude the formation of polyboranes through condensation reactions.
Structure and dynamics of
H atom disorder and rapid reorientation of NH4+ and BH4− ions in hydrogen storage material NH4BH4.
activation by sulfido-bridged dinuclear Ru/ Ge complexes: insight into the [ NiFe] hydrogenase unready state
Molecular H2 was activated by S/SH bridged dinuclear Ru/Ge complexes, which model the activation process of the “unready” state of [NiFe] hydrogenase.
Diiron species containing a cyclic PPh2NPh2 diphosphine related to the [FeFe]H2ases active site
Preliminary investigations of proton and electron transfers on new dissymmetrically disubstituted diiron dithiolate species [Fe2(CO)4(κ2-PPh2NPh2)(μ-pdt)] have been done.
Double addition of H2 to transition metal–
borane complexes: a ‘ hydride shuttle’ process between boron and transition metal centres
The addition of H2 across a transition metal–borane bond is reported for the first time. Successive hydrogen addition to a rhodium–norbornadiene complex leads to the elimination of the organic species and a recharging of the boron–hydrogen bond providing active hydrogenation catalysts.
diammoniate of diborane: crystal structure and hydrogen release
The crystal structure of the diammoniate of diborane is presented for the first time since its discovery in 1923.
oxidation catalysis by a nickel diphosphine complex with pendant tert-butyl amines
A bis-diphosphine nickel complex with tert-butyl functionalized pendant amines functions as a highly active electrocatalyst for the oxidation of hydrogen in the presence of base.
dihydrogen cleavage by a bifunctional frustrated pyrazolylborane Lewis pair
A bifunctional pyrazolylborane is introduced that is capable of heterolytic dihydrogen activation at ambient temperature and pressure; the resulting zwitterionic dihydro congener represents a potential metal-free hydrogenation catalyst.
Gas pressure effects on the rates of
catalytic H2 oxidation by hydrogenases
Investigations of an observation that the rate of H2 oxidation by a hydrogenase decreases as the dissolved gas concentration increases.
Altered thermodynamic and kinetic properties of MgH2 infiltrated in microporous scaffold
The enthalpy of formation of MgH2 is lowered by 11 kJ mol−1 if the hydride particles are smaller than 3 nm.
hydriding/ dehydriding reactions of CaPd
Multimode hydriding/dehydriding reactions of CaPd proceed via hydrogen solution/dissolution and phase decomposition/recombination over wide temperature ranges.
hydrogen production from water in self-assembled supramolecular iridium– cobalt systems
Self-assembled supramolecular photocatalytic systems produced H2 in aqueous solutions upon visible light irradiation.
Electric field induced
activation of H2—Can DFT do the job?
The applicability of different density functional methods to the problem of dihydrogen dissociation in an electric field as a model for FLP activation and the bi-radical character of the reaction are investigated.
Chain mechanism for exchange of D2 with a ruthenium hydride
The ruthenium hydride of (Ar4CpOH)Ru(CO)2H exchanges cleanly and rapidly with D2 at room temperature to generate the ruthenium deuteride. A chain mechanism is proposed to explain the much more rapid exchange of RuH/D2 than RuCO exchange with 13CO.
Azulene based metal–organic frameworks for strong adsorption of H2
MOFs comprised of internally polarized 1,3-azulenedicarboxylate were synthesized. The guest free MOF exhibits strong MOF-H2 interactions (7.8–6.8 kJ mol−1) revealing the significant impact of internally polarized azulene backbone to stabilized H2 molecules in the framework.
Hydrogen generation by electrolysis of liquid ammonia
Hydrogen gas is generated by the electrolysis of liquid ammonia which has high hydrogen capacity of 17.8 mass%.
water reduction with cyclometalated Ir(III) 4-vinyl-2,2′-bipyridine complexes
Novel [Ir(C⁁N)2(N⁁N)]+ complexes with N⁁N ligands containing vinyl groups were synthesized resulting in quintupled turn-over numbers for the photocatalytic hydrogen production compared to analogous non-vinyl compounds.
Thermodynamic and kinetic destabilization in LiBH4/Mg2NiH4: promise for borohydride-based
The LiBH4/Mg2NiH4 hydride system reversibly cycles hydrogen via a new reaction path with exceptionally low enthalpy and entropy.
nickel- iridium nanocatalysts for hydrogen generation by decomposition of hydrous hydrazine
Bimetallic NiIr alloy nanocatalysts exhibit 100% H2 selectivity for complete decomposition of hydrous hydrazine at room temperature.
Parahydrogen-induced polarization in alkyne hydrogenation catalyzed by Pd nanoparticles embedded in a supported ionic liquid phase
Parahydrogen-induced polarization was observed in the gas phase heterogeneous hydrogenation of propyne catalyzed by Pd0 nanoparticles embedded in an ionic liquid phase supported on activated carbon fibers (Pd0/SILP/ACF). The essential role of the ionic liquid is demonstrated.
reductions of N-heterocycles via Lewis acid catalyzed hydrogenation
N-Heterocycles are reduced in the presence of a catalytic amount of the borane B(C6F5)3 and H2.
DFT characterization of the reaction pathways for terminal- to
μ-hydride isomerisation in synthetic models of the [FeFe]-hydrogenase active site
The mechanism of terminal- to μ-hydride isomerisation in models of synthetic complexes resembling the [FeFe]-hydrogenase active site has been elucidated by DFT calculations.
assembly of an H-cluster analogue within a functionalised poly(pyrrole) matrix
Building an H-cluster analogue within a poly(pyrrole) modified electrode.
Reversibility of the
hydrogen desorption from LiBH4: a synergetic effect of nanoconfinement and Ni addition
Reversible hydrogen uptake in LiBH4 is greatly enhanced by a combined effect of nanoconfinement in mesoporous carbon and Ni addition.
hydrogenation of molecules with polar bonds catalyzed by a ruthenium(II) complex bearing a chelating N-heterocyclic carbene with a primary amine donor
A ruthenium(II) complex bearing a chelating N-heterocyclic carbene with an NH2 group (C–NH2) is a catalyst for the H2-hydrogenation of polar bonds in basic solution.
About this collection
This web-based themed issue showcases high quality articles covering all aspects of hydrogen generation, storage and activation. The invited, peer-reviewed articles highlight cutting-edge contributions by international leaders and celebrate current achievements and future perspectives in this exciting field of research.
The guest editors of this issue are Ferdi Schüth, Daniel DuBois, Mary DuBois and Douglas Stephan.
Articles in this web themed issue will be added to the list below as soon as possible, after they are published. Please return to this page frequently to see this collection grow.