Catalytic H2 Evolution Research Articles

Plasmonic Mo-doped HNb3O8 nanosheets with tunable energy band structures for photothermal catalytic H2 evolution in Full Solar Spectrum

Ultrathin Mo-HNb3O8 nanosheets were synthesized by a facile hydrothermal process. Introducing low-valence Mo and oxygen vacancies into the pristine HNb3O8 nanosheets can modulate the band structure and induce the localized...

Microbial Electrosynthesis Using 3D Bioprinting of Sporomusa ovata on Copper, Stainless-Steel, and Titanium Cathodes for CO2 Reduction

Acetate can be produced from carbon dioxide (CO2) and electricity using bacteria at the cathode of microbial electrosynthesis (MES). This process relies on electrolytically-produced hydrogen (H2). However, the low solubility of H2 can limit the process. Using metal cathodes to generate H2 at a high rate can improve MES. Immobilizing bacteria on the metal cathode can further proliferate the H2 availability to the bacteria. In this study, we investigated the performances of 3D bioprinting of Sporomusa ovata on three metal meshes—copper (Cu), stainless steel (SS), and titanium (Ti), when used individually as a cathode in MES. Bacterial cells were immobilized on the metal using a 3D bioprinter with alginate hydrogel ink. The bioprinted Ti mesh exhibited higher acetate production (53 ± 19 g/m2/d) at −0.8 V vs. Ag/AgCl as compared to other metal cathodes. More than 9 g/L of acetate was achieved with bioprinted Ti, and the least amount was obtained with bioprinted Cu. Although all three metals are known for catalyzing H2 evolution, the lower biocompatibility and chemical stability of Cu hampered its performance. Stable and biocompatible Ti supported the bioprinted S. ovata effectively. Bioprinting of synthetic biofilm on H2-evolving metal cathodes can provide high-performing and robust biocathodes for further application of MES.

Influences of Partial Destruction of Ti-MOFs on Photo(electro)catalytic H2 Evolution by Dominating Role of Charge Carrier Trapping over Surface Area.

The design of water-stable photo and electrocatalysts of metal-organic frameworks (MOFs) for its promising catalytic applications at long-term irradiations or persisted current loads is extremely necessary but still remains as challenging. A limited number of reports on Ti-MOF-based catalysts for water splitting are only available to explain and understand the correlation between the nature of materials and MOFs array. Herein, spherical Ti-MOFs and corresponding partially annealed hollow core-shell Ti-MOFs (Ti-MOF/D) are designed and the correlation with their photo(electro)catalytic water splitting performance is evaluated. The switchable valence state of Ti for the Ti-MOF as a function of molecular bonding is the possible reason behind the observed photocatalytic hydrogen generation and light-harvesting ability of the system. Besides, the defect state, solid core-shell mesoporous structure, and active sites of Ti-MOF help to trap the charge carriers and the reduction of the recombination process. This phenomenon is absent for hollow core-shells Ti-MOF/D spheres due to the rigid TiO2 outer surface although there is a contradiction in surface area with Ti-MOF. Considering the diversity of Ti-MOF and Ti-MOF/D, further novel research can be designed using this way to manipulate their properties as per the requirements.

Exploring the Sub-nanoscale Structure of Cobalt Molybdenum Sulfide and the Role of a Cobalt Promoter in Catalytic Hydrogen Evolution.

Cobalt-promoted molybdenum sulfide (CoMoS) is known as a promising catalyst for H2 evolution reaction and hydrogen desulfurization reaction. This material exhibits superior catalytic activity as compared to its pristine molybdenum sulfide counterpart. However, revealing the actual structure of cobalt-promoted molybdenum sulfide as well as the plausible contribution of a cobalt promoter is still challenging, especially when the material has an amorphous nature. Herein, we report, for the first time, on the use of positron annihilation spectroscopy (PAS), being a nondestructive nuclear radiation-based method, to visualize the position of a Co promoter within the structure of MoS at the atomic scale, which is inaccessible by conventional characterization tools. It is found that at low concentrations, a Co atom occupies preferably the Mo-vacancies, thus generating the ternary phase CoMoS whose structure is composed of a Co-S-Mo building block. Increasing the Co concentration, e.g., a Co/Mo molar ratio of higher than 1.12/1, leads to the occupation of both Mo-vacancies and S-vacancies by Co. In this case, secondary phases such as MoS and CoS are also produced together with the CoMoS one. Combining the PAS and electrochemical analyses, we highlight the important contribution of a Co promoter to enhancing the catalytic H2 evolution activity. Having more Co promoter in the Mo-vacancies promotes the H2 evolution rate, whereas having Co in the S-vacancies causes a drop in H2 evolution ability. Furthermore, the occupation of Co to the S-vacancies leads also to the destabilization of the CoMoS catalyst, resulting in a rapid degradation of catalytic activity.

Ru/Pt@BSA nanoparticles for efficient photo-catalytic oxidation of NAD(P)H and targeted cancer treatment under hypoxic conditions

Photo-catalytic oxidation of intracellular nicotinamide adenine dinucleotide (2′-phosphate) (NAD(P)H) has attracted much attention for cancer therapy. However, the general oxygen-dependent mechanism heavily depresses the efficacy in hypoxic tumors. To solve this problem, herein platinum nanoparticles (Pt NPs) with catalase-like (CAT-like) and catalytic H2 evolution activities were introduced as a powerful assistant to enhance the photo-catalytic NAD(P)H oxidation of Ru1 ([Ru(phen)2(PIP-OCH3)]2+, phen = 1,10-phenanthroline, PIP-OCH3 = 2-(4‑methoxy phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline) under hypoxic and even oxygen-free conditions. Firstly, Pt NPs can transform the original and in situ formed H2O2 once again into O2 by the CAT-like activity, thus relieving tumor hypoxia and realizing cyclic utilization (at least in part) of the precious oxygen in hypoxia. Secondly, Pt NPs can also be served as H2 evolution catalysts while using Ru1 as the photosensitizer and NAD(P)H as the electron and proton donor. In this process, NAD(P)H is oxidized without the participation of oxygen, which can provide an effective way even under oxygen-free conditions. Via co-encapsulation of Ru1 and Pt NPs in bovine serum albumin (BSA) with tumor targeting ability, the resultant Ru/Pt@BSA could photo-catalyze intracellular NAD(P)H oxidation under hypoxic conditions (3% O2), and exhibited an efficient and selective anticancer activity both in vitro and in vivo. Our results may provide new sights for efficient and targeted cancer treatment under hypoxic conditions.

Engineering Single-Atom Sites into Pore-Confined Nanospaces of Porphyrinic Metal-Organic Frameworks for the Highly Efficient Photocatalytic Hydrogen Evolution Reaction.

As a type of heterogeneous catalyst expected for the maximum atom efficiency, a series of single-atom catalysts (SACs) containing spatially isolated metal single atoms (M-SAs) have been successfully prepared by confining M-SAs in the pore-nanospaces of porphyrinic metal-organic frameworks (MOFs). The prepared MOF composites of M-SAs@Pd-PCN-222-NH2 (M = Pt, Ir, Au, and Ru) display exceptionally high and persistent efficiency in the photocatalytic hydrogen evolution reaction with a turnover number (TON) of up to 21713 in 32 h and a beginning/lasting turnover frequency (TOF) larger than 1200/600 h-1 based on M-SAs under visible light irradiation (λ ≥ 420 nm). The photo-/electrochemical property studies and density functional theory calculations disclose that the close proximity of the catalytically active Pt-SAs to the Pd-porphyrin photosensitizers with the confinement and stabilization effect by chemical binding could accelerate electron-hole separation and charge transfer in pore-nanospaces, thus promoting the catalytic H2 evolution reaction with lasting effectiveness.

Palladium complexes bearing calixpyrrole ligands with pendant hydrogen bond donors: Synthesis, structural characterization, electrochemistry and dihydrogen evolution

A series of three calixpyrrole ligands (1a-c) with pendant nitrogen-based hydrogen bond donors, R, were synthesized and coordinated to palladium to produce metal complexes (2a-c), where R = NH2 (a); NHC(O)CH3 (b); or NHC(O)OC(CH3)3 (c). The calixpyrrole compounds were generated using a Schiff-base reaction starting with 5,5′-diformyl-2,2′-diphenyldipyrromethane and an aniline precursor. The deprotonated calixpyrrole species were subsequently bound to palladium to generate distorted square planar complexes. The pendant groups were not coordinated to the metal with Pd-N distances of 3.36 to 4.79 Å. The electrochemical properties of the palladium complexes were also explored, and 2a-c displayed two irreversible oxidations above 0.0 V vs ferrocene/ferrocenium (Fc/Fc+), as well as two irreversible reductions below −0.70 V vs Fc/Fc+. Interestingly, the free ligands showed similar electrochemical features, suggesting redox non-innocence. Preliminary reactivity studies indicated the palladium complexes did not activate small molecules, but they did catalyze H2 evolution in the presence of acid. The onset of catalysis for 2a-c was approximately 0.4–0.5 V more positive than a glassy carbon electrode, and the active species could undergo 500 scans without significant changes in activity. The catalysts were found to be heterogeneous in nature and adsorbed onto the working electrode.

Piezoelectric polarization of BiOCl via capturing mechanical energy for catalytic H2 evolution

Exploring a green and sustainable method for catalytic water splitting to hydrogen (H2) holds a great potential towards solving the looming global environment and energy crisis. Herein, a piezoelectric catalytic H2 evolution reaction (HER), using a sheet-like BiOCl as the catalyst, can convert mechanical energy into clean hydrogen energy. A high yield of HER (975.4 µmol g−1h−1) was reached by the ultrasound-based piezoelectric catalysis, exhibiting the excellent piezoelectric catalytic activity of as-synthesized BiOCl. Under mechanical vibration of ultrasound, sheet-like BiOCl would deform, inducing piezoelectric polarization and generation of abundant free polarized-electrons on the surface for redox reactions. BiOCl with continued ultrasonic vibration not only achieves durability HER, but also simultaneously utilizes electrons and holes to form reactive oxygen species (ROS) for a high-efficient degradation rate (98%) of organic antibiotic pollutants (sulfamethazine) removal in 120 min. This work provides a new idea for promoting environmental purification and developing clean hydrogen energy.

A 3D flower-like WC with large capacitance as efficient co-catalyst in photocatalytic H2 evolution

Non-noble metal co-catalysts can promote photo-excited charge separation of semiconductor and act as active sites for proton catalytic H2 evolution. However, how to judge which function non-noble metal co-catalyst has is not clear. Here, we reported a 3D flower-like WC (WC–F) which shows outstanding activity (24502 μmol/h/g) on CdS in photocatalytic H2 evolution. WC–F has the largest specific capacitance (12.07 F/g), which contributes to the largest electron storage capability. The integration of noble metal Pd and WC tests demonstrated WC–F has the largest proton reduction catalysis ability. Significantly, composite co-catalyst Pd/WC–F on CdS shows slightly higher (1.16 times) activity than WC–F/CdS, which means most of photoexcited electrons on WC–F have been consumed and reaction with protons to produce hydrogen. Thus, two judgement methods for both charges storage and protons catalysis were put forward.

Effect of Lewis Basic Amine Site on Proton Reduction Activity of NNN‐Co Pincer Complex

Electrochemical proton reduction is a promising energy storage method because H2 molecule has a simple structure with a relatively low potential energy. Current interest in hydrogen catalysts has increased research efforts on synthetic analogs of hydrogenase active sites. In this study, we demonstrated the electrochemical H2 evolution reactivity of [NNNR‐Co(CH3CN)3]2+ (R  CH2 (1b), NCH3 (2b)) complexes and examined a proton‐relay process in the H2 evolution reaction (HER). Upon one‐electron reduction, the Co(II) ion center in a high‐spin state dissociated a CH3CN ligand, while opening a reaction site. Cyclic voltammograms of the Co complexes indicated quasi‐reversible Co(II/I) redox behaviors, and both complexes 1b and 2b showed catalytic H2 evolution activity. Interestingly, 2b, assisted by a proton‐relaying NCH3 group, exhibited more efficient catalytic activity than 1b.

{Cu8} Cluster-Sandwiched Polyoxotungstates and Their Polymers: Syntheses, Structures, and Properties.

Four inorganic-organic hybrid octa-Cu cluster sandwiched polyoxotungstates (POTs), [Cu8(H2O)2(en)4(B-α-H2SiW9O34)2] (1), [Cu8(H2O)2(en)4(B-α-H2GeW9O34)2] (2), K2[Cu8(en)4(B-α-HSiW9O34)2]·6H2O (3), and K2[Cu8(en)4(B-α-HGeW9O34)2]·2H2O (4) (en = ethylenediamine), were hydrothermally made and characterized by single-crystal X-ray diffraction, infrared spectra, powder X-ray diffraction, and thermogravimetric analysis, respectively. Structure analysis reveals that the polyoxoanion of 1/2 is a discrete dimer built by two trivalent Keggin [B-α-XW9O34]10- (X = Si/Ge) fragments and one octa-Cu cluster, whereas 3 and 4 display a two-dimensional network built by octa-Cu-sandwiched POT units via substitution of coordinated water on polyanions of 1 and 2 and further expand into a three-dimensional framework via K cation bridges. Ultraviolet-visible diffuse reflectance spectra reveal that 1-4 are potential semiconductor materials. Moreover, its visible light-driven catalytic H2 evolution activity, electrochemical properties, catalysis for oxygenation reactions of thioethers, and magnetic behaviors have been investigated in detail.

N2 plasma treatment TiO2 nanosheets for enhanced visible light-driven photocatalysis

An enhancement of the photocatalytic activity of Titanium dioxide nanosheets (TiO2 NFs) by N2 plasma (N-plasma) treatment has been suggested. TiO2 NFs was synthesized by a solvothermal method and treated with N-plasma at atmospheric pressure. Then the as-prepared TiO2 and N-plasma treated TiO2 (N-TiO2) NFs photocatalyst were extensively characterized. Interestingly, more oxygen vacancy and Ti3+ ions were found in the N-TiO2 NFs. Meanwhile, Ti3+ ions form the Ti3+ self-doped system, which causing the light absorption range enhanced. The catalytic H2 evolution of N-TiO2 NFs at a rate of 8.1 mmol g−1 h−1, which is 14.85 times higher than that of the pristine TiO2 NFs. These results might suggest new views for the photoactivity of TiO2 NFs and provide a kind of feasibility for other metal oxides in the photocatalytic field.

Co/MoS2 nanocomposite catalyzed H2 evolution upon dimethylamine-borane hydrolysis and in situ tandem reaction

Since dimethylamine-borane ($ 463/kg) is much cheaper than ammonia borane ($ 13,921/kg), the hydrolysis of dimethylamine-borane catalyzed by transition metal nanocatalysts has long been proposed as a viable opportunity for hydrogen evolution, but it often required noble metals nanocomposites, such as Pt, Rh and Ru. Herein, we first report the ultrafine non-noble metal nanoparticles supported on MoS2 nanosheet (including Fe/MoS2, Co/MoS2, Ni/MoS2 and Cu/MoS2) for the H2 evolution from hydrolysis of dimethyl amine-borane (DMAB). Among them, Co/MoS2 is found to be more efficient than others for the H2 evolution, with the TOF of 374 mol(H2)•molcat−1•h−1. Kinetic isotopic experiment and the tandem reaction have confirmed that H2 evolution by using H atoms in water.

A Win-Loss Interaction on Fe0 Between Methanogens and Acetogens From a Climate Lake.

Diverse physiological groups congregate into environmental corrosive biofilms, yet the interspecies interactions between these corrosive physiological groups are seldom examined. We, therefore, explored Fe0-dependent cross-group interactions between acetogens and methanogens from lake sediments. On Fe0, acetogens were more corrosive and metabolically active when decoupled from methanogens, whereas methanogens were more metabolically active when coupled with acetogens. This suggests an opportunistic (win–loss) interaction on Fe0 between acetogens (loss) and methanogens (win). Clostridia and Methanobacterium were the major candidates doing acetogenesis and methanogenesis after four transfers (metagenome sequencing) and the only groups detected after 11 transfers (amplicon sequencing) on Fe0. Since abiotic H2 failed to explain the high metabolic rates on Fe0, we examined whether cell exudates (spent media filtrate) promoted the H2-evolving reaction on Fe0 above abiotic controls. Undeniably, spent media filtrate generated three- to four-fold more H2 than abiotic controls, which could be partly explained by thermolabile enzymes and partly by non-thermolabile constituents released by cells. Next, we examined the metagenome for candidate enzymes/shuttles that could catalyze H2 evolution from Fe0 and found candidate H2-evolving hydrogenases and an almost complete pathway for flavin biosynthesis in Clostridium. Clostridial ferredoxin-dependent [FeFe]-hydrogenases may be catalyzing the H2-evolving reaction on Fe0, explaining the significant H2 evolved by spent media exposed to Fe0. It is typical of Clostridia to secrete enzymes and other small molecules for lytic purposes. Here, they may secrete such molecules to enhance their own electron uptake from extracellular electron donors but indirectly make their H2-consuming neighbors—Methanobacterium—fare five times better in their presence. The particular enzymes and constituents promoting H2 evolution from Fe0 remain to be determined. However, we postulate that in a static environment like corrosive crust biofilms in lake sediments, less corrosive methanogens like Methanobacterium could extend corrosion long after acetogenesis ceased, by exploiting the constituents secreted by acetogens.

Exceptional Cocatalyst-Free Photo-Enhanced Piezocatalytic Hydrogen Evolution of Carbon Nitride Nanosheets from Strong In-Plane Polarization.

Utilizing mechanical energy to produce hydrogen is emerging as a promising way to generate renewable energy, but is challenged by low efficiency and scanty cognition. In this work, graphitic carbon nitride (g-C3 N4 ) with an atomically thin sheet-like structure is applied for prominent piezocatalytic and photo-enhanced piezocatalytic H2 production. It is revealed that the anomalous piezoelectricity in g-C3 N4 originates from the strong in-plane polarization along the a-axis, contributed by the superimposed polar tri-s-triazine units and flexoelectric effect derived from the structured triangular cavities, which provides powerful electrochemical driving force for the water reduction reaction. Furthermore, the photo-enhanced charge transfer enables g-C3 N4 nanosheets to reserve more energized polarization charges to fully participate in the reaction at the surface reactive sites enriched by strain-induced carbon vacancies. Without any cocatalysts, an exceptional photo-piezocatalytic H2 evolution rate of 12.16 mmol g-1 h-1 is delivered by the g-C3 N4 nanosheets, far exceeding that of previously reported piezocatalysts and g-C3 N4 photocatalysts. Further, high pure-water-splitting performance with production of the value-added oxidation product H2 O2 via photo-piezocatalysis is also disclosed. This work not only exposes the potential of g-C3 N4 as a piezo-semiconductor for catalytic H2 evolution, but also breaks a new ground for the conversion of solar and mechanical energy by photomediated piezocatalytic reaction.

Heteroleptic thiolate diamine nickel complexes: Noble-free-metal catalysts in electrocatalytic and light-driven hydrogen evolution reaction

Three mononuclear heteroleptic nickel complexes bearing the non-innocent o-aminobenzenethiolate (2-amnt) ligand and different diamine ligands, namely, [Ni(2-amnt)(o-phen)] (o-phen = o-phenylenediamine) (1), [Ni(2-amnt)(3,4-daba)] (3,4-daba = 3, 4-diamino benzoic acid) (2) and [Ni(2-amnt)(dmnt)] (dmnt = diaminomaleonitrile) (3), were synthesized and characterized. Complexes 1–3 are active homogeneous proton reduction electrocatalysts in dimethylformamide with trifluoroacetic acid as a proton source. All the three complexes are tested in light-driven hydrogen evolution reaction, indicating different catalytic efficiencies. Thus, although complex 3 indicates no catalytic action, both complexes 1 and 2 catalyze H2 evolution in water-dimethylformamide solutions using fluorescein (Fl) as a photosensitizer. Complex 2 acts as a homogeneous catalyst reached 834 turnovers (TON); whereas 1, despite being active in hydrogen evolution reaction (HER), decomposes to form nanomaterials. DFT calculations combined with electrochemical and spectroscopic data were employed to investigate the catalytic mechanism for H2 formation as well as to unravel the key factors that influence the relative catalytic efficiencies. The proposed catalytic pathway involves ligand-based reduction and protonation steps followed by the formation of a nickel-hydride intermediate that reacts with a solution proton to generate H2 via a very low energy transition state.

Electrochemical behaviors of a pincer-type NNN-Fe complex and catalytic H2 evolution activity.

We describe electrochemical reactivity of a pincer-type [NNN-Fe(tBuNC)3](ClO4)2 complex. Upon electron reduction, the Fe(i) species experienced disproportionation to Fe(0) and Fe(ii). An electron-reduced Fe center dissociated a tBuNC ligand to make an open coordination site, where a proton could be transferred. The low-spin Fe center, assisted by isocyanide and a pyridine-based NNN-pincer ligand, catalyzed efficiently the proton reduction reaction. Also, a Lewis basic amine site in the side 'arm' of the NNN-pincer ligand lowered the free energy for the protonation of an Fe center during the proton reduction process. DFT calculations provided insight into a plausible catalytic pathway.

Phenyl-Bridged Graphitic Carbon Nitride with a Porous and Hollow Sphere Structure to Enhance Dissociation of Photogenerated Charge Carriers and Visible-Light-Driven H2 Generation.

Graphitic carbon nitride (CN) suffers from rapid recombination of photoexcited charges due to the existing highly symmetrical tri-s-triazine ring and long charge diffusion path, resulting in moderate photocatalytic activity. The bridged phenyl embedded in the CN structure was used to reduce the symmetry of the tri-s-triazine ring. In addition, the CN material was constructed with a porous and hollow sphere structure to shorten the diffusion path of charge carriers. Herein, simple thermal polymerization of a trimesic acid-doped melamine-cyanuric acid (MCA) supramolecular was employed to construct phenyl-bridged graphitic carbon nitride (Ph-CN-MCA) with a hollow sphere structure composed of porous nanosheets for visible-light catalytic H2 evolution. The porous and hollow sphere-structured Ph-CN-MCA possessed increased degree of polymerization, more negative conduction band potential, enlarged Brunauer-Emmett-Teller (BET) surface area, and shortened charge diffusion path. In addition, bridged phenyl embedded in the Ph-CN-MCA structure not only accelerated the dissociation of photogenerated carriers but also narrowed the band gap and extended the visible-light absorption. Further, the separated highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of Ph-CN-MCA facilitated the spatial dissociation of photogenerated charges, which was also confirmed by theoretical calculations. As a consequence, compared with the reference CN-MA catalyst prepared from melamine, Ph-CN-MCA showed approximately 48.42 times the photocatalytic H2 evolution under visible-light irradiation. The developed synthetic method herein highlights that phenyl-bridged graphitic carbon nitride with a porous and hollow sphere structure could provide an efficient platform to boost the dissociation of photoexcited charge carriers and photocatalytic H2 evolution.

Investigation on the Growth Mechanism of Cu2MoS4 Nanotube, Nanoplate and its use as a Catalyst for Hydrogen Evolution in Water

Cu2 MoS4 is a ternary transition-metal sulfide that shows great potential in the field of energy conversion and storage, namely catalytic H2 evolution in water and Li-, Na- or Mg-ion battery. In this work, we report on a growth mechanism of the single-crystalline Cu2 MoS4 nanotube from (NH4 )2 MoS4 salt and Cu2 O nanoparticle. By probing the nature and morphology of solid products generated in function of reaction conditions we find that the crystalline Cu(NH4 )MoS4 nanorod is first generated at ambient conditions. The nanorod is then converted into Cu2 MoS4 nanotube under hydrothermal treatment due to the Kirkendall effect or a selective etching of the Cu2 MoS4 core. Extending the hydrothermal treatment causes a collapse of nanotube generating Cu2 MoS4 nanoplate. The catalytic activities of these sulfides are investigated. The Cu2 MoS4 shows superior catalytic activity to that of Cu(NH4 )MoS4 . Catalytic performance of the former largely depends on its morphology. The nanoplate shows superior catalytic activity to the nanotube, thanks to its higher specific electrochemical surface area.

Dehydrogenation of amine–boranes catalyzed by a [formula omitted] pincer iridium complex

Dibenzobarrelene-based PC s p 3 P pincer iridium complex bearing dangling CH2OH groups, ( ( PC s p 3 P CH 2 OH ) IrH ( Cl ) , catalyzes the dehydrogenation of amine–boranes at the reaction rate changing counter intuitively in the order: Me2NH·BH3 > > ButNH2·BH3 > NH3·BH3. The spectral (IR and NMR) data and DFT/M06 calculations have revealed that the binding of amine–boranes to the dangling OH group leads to an additional stabilization of the Ir···OH bond, thus hampering the dehydrogenation reaction, whereas the amine–borane coordination to iridium entails a fac- to mer-transformation of the complex and initiates the catalytic H2 evolution.