Hydrogenation Pathway Research Articles

Amino Acid-Based Ionic Liquids-Aided CO2 Hydrogenation to Methanol.

This study explored the use of amino acid-based ionic liquids to facilitate the conversion of carbon dioxide (CO2) into methanol through catalytic hydrogenation. Combining tetrabutylammonium L-argininate (TBA⋅Arg) with the ruthenium Ru-MACHO-BH complex allowed achieving significant yields of methanol under optimized conditions, with a turnover number (TON) up to 700. By systematically varying key reaction parameters, we demonstrated that the TBA⋅Arg ionic liquid promotes the efficient hydrogenation pathway leading to methanol formation, thus offering a sustainable approach to CO2 valorization. These findings underscore the potential of amino acid-based ionic liquids in catalyzing the transformation of CO2 into valuable chemicals, contributing to carbon mitigation efforts.

Size and Morphology Dependent Activity of Cu Clusters for CO2 Activation and Reduction: A First Principles Investigation.

Various Cu-based materials in diverse forms have been investigated as efficient catalysts for electrochemical reduction of CO2; however, they suffer from issues such as higher over potential and poor selectivity. The activity and selectivity of CO2 electro reduction have been shown to change significantly when the surface morphology (steps, kinks, and edges) of these catalysts is altered. In light of this, size and morphology dependent activity of selected copper clusters, Cun (n=2-20) have been evaluated for the activation and reduction of CO2 molecule. The phase-space of these copper clusters is rich in conformations of distinct morphologies starting from planar, 2D geometries to prolate-shaped geometries and also high-symmetry structures. The binding efficiency and the activation of CO2 are highest for medium sized clusters (n=9-17) with prolate-morphologies as compared to small or larger sized CunCO2 clusters that are existing mainly as planar (triangular, tetragonal etc.) or highly-symmetric geometries (icosahedron, capped-icosahedron etc.), respectively. The best performing (prolate-shaped) CunCO2 conformations are quite fluxional and also they are thermally stable, as demonstrated by the molecular dynamics simulations. Furthermore, on these CunCO2 conformations, the step-by-step hydrogenation pathways of CO2 to produce value-added products like methanol, formic acid, and methane are exceptionally favorable and energy-efficient.

Shifting hydrogenation pathway via electronic activation for efficient nitrate electroreduction to ammonia in sewages

Shifting hydrogenation pathway via electronic activation for efficient nitrate electroreduction to ammonia in sewages

Assessment of a coupled electricity and hydrogen sector in the Texas energy system in 2050

Due to its ability to reduce emissions in the hard-to-abate sectors, hydrogen is expected to play a significant role in future energy systems. This study modifies a sector-coupled dynamic modeling framework for electricity and hydrogen by including policy constraints, carbon prices, and possible hydrogen pathways and applies it to Texas in 2050. The impact of financial policies, including the US clean hydrogen production tax credit, on required infrastructure and costs are explored. Due to low natural gas prices, financial levers are necessary to promote low-carbon hydrogen production as the optimized solution. The Levelized Costs of Hydrogen are found to be $1.50/kg in the base case (primarily via steam methane reformation production) and lie between $2.10 - 3.10/kg when production is via renewable electrolysis. The supporting infrastructure required to supply those volumes of renewable hydrogen is immense. The hydrogen tax credit was found to be enough to drive production via electrolysis.

Comparing green hydrogen and green ammonia as energy carriers in utility-scale transport and subsurface storage

Many of the challenges associated with utility-scale hydrogen transport and storage relate to its low density, high diffusivity, and the risk of hydrogen embrittlement, motivating consideration to integrating ammonia as an energy carrier. Compared to hydrogen, ammonia is more compatible with pipeline materials and delivers energy at higher density. Ammonia is also a mature industry with a greater extent of established pipeline networks and regulations that may accelerate hydrogen transitions and penetration in energy grids. However, converting hydrogen produced by renewable-driven electrolysis into ammonia (and back to hydrogen, depending on end use) complicates logistics, and associated energy and resource demands may offset the green hydrogen's carbon neutrality. This work outlines core considerations for the use of hydrogen vs. ammonia during transport and storage operations, with an emphasis on green hydrogen or green ammonia pathways coupled to pipeline transport and underground storage. We compare tradeoffs in pipeline infrastructure and operations; subsurface storage options; and project economics. We also evaluate round-trip efficiencies (RTE) for both pathways, which indicate that hydrogen is more attractive from an energy efficiency perspective for hydrogen end-use applications due to the efficiency penalties of initial ammonia synthesis and subsequent cracking, but RTE's for ammonia transport and storage are comparable to hydrogen for direct use or ammonia-to-power systems. The tradeoffs presented in this work would need to be considered on a case-by-case basis, but indicate that selective use of ammonia as an energy-dense hydrogen carrier could support decarbonization goals in industry and hydrogen economies.

A novel hexagonal prism of Zr-based MOF@ZnIn2S4 core−shell nanorod as an efficient photocatalyst for hydrogen evolution

Photocatalytic water splitting is a commonly used pathway for hydrogen (H2) production, and it is crucial to develop highly active ZnIn2S4 (ZIS)-based photocatalytic systems. In recent years, metal-organic frameworks (MOFs) are also of great interest in the fields of energy production and environmental remediation. Therefore, this study primarily focuses on the fabrication of a series of heterojunction hexagonal prism-shaped Zr-based MOF@ZIS core-shell nanorods through a simple solvothermal method, in which ZIS nanosheets are highly distributed on the surface of the Zr-based MOF (NU-1000). The photocatalytic activities of the resulting materials were evaluated under visible light illumination (λ ≥ 400 nm) by combining different contents of NU-1000 with ZIS. The H2 evolution results demonstrate that the optimal content of NU-1000 corresponds to a photocatalytic H2 production rate of 8.53 mmol g−1 h−1, which is 5.3 times higher than that of pure ZIS. The enhanced photocatalytic activity of the NU-1000@ZIS (NUZ) heterojunction can be attributed to the incorporation of the NU-1000, which provides abundant active sites due to its larger specific surface area. Additionally, the well-matched band structure between the NU-1000 and ZIS is beneficial to efficiently transfer and separate the photogenerated charge carriers. Furthermore, the NUZ core-shell nanorods exhibit excellent stability, offering a new approach for the fabrication of composite photocatalysts by combining MOF-based and ZIS in the field of photocatalytic H2 production.

Cobalt-Catalyzed Divergence in C(sp3)-H Functionalization of 9H-Fluorene: A Streamlined Approach Utilizing Alcohols.

Sustainable chemical production demands the creation of innovative catalysts and catalytic technologies. While the development of coherent and robust catalytic systems using earth-abundant transition metals is essential, it remains a significant challenge. Herein, an expedient divergence strategy for tandem dehydrogenative C(sp3)-H alkylation and cyclization reactions of 9H-fluorene using a newly developed N,N-bidentate cobalt catalytic system is developed. This method capitalizes on the use of abundant and readily accessible alcohol. Demonstrating wide-ranging applicability, the catalytic protocol successfully integrated a diverse array of fluorenes and alcohols. This includes benzylic, heteroaromatic, and aliphatic primary and secondary alcohols, amassing a total of 75 distinct examples. When applied to sterically bulky alcohols, the reaction preferentially undergoes alkenylation, yielding a tetrasubstituted olefin as the main product. In the case of diols, the expected outcome is Dual-fluorescence at both terminal positions. This process leads to difluorination, followed by a cyclization step, culminating in the formation of a relatively unprecedented spiro compound. The scalability of this method has been validated through gram-scale synthesis. Control experiments have shed light on the reaction mechanism, indicating that it progresses through an unsaturated intermediate and adheres to the borrowing hydrogen pathway.

Catalytic N-Alkylation of (Hetero)Aromatic Amines and Tandem Annulation Reactions.

A general and practical approach for N-alkylation of heteroaromatic amines with heteroaromatic alcohols is always challenging and rarely reported. Here, we designed and synthesized phosphine-free, robust, and efficient N,N-bidentate-Co(II) complexes for a universal N-alkylation of amines strategy. This present catalytic methodology can be applied to a wide range of substrates by varying alcohols, including aryl, aliphatic, acyclic, and cyclic groups, with heteroaromatic amines such as aminopyridine, 2-aminopyrimidine, and aminoquinoline to provide diverse monoalkylated organonitrogen compounds in good to excellent yields (108 examples). In addition, the utility of the developed catalytic protocol was also extended successfully for the dehydrogenative synthesis of biologically important quinoline derivatives (11 examples). Particularly, 8-aminoquinoline reacted differently with tandem N-alkylated-transfer hydrogenative byproduct (N-benzyl-1,2,3,4-tetrahydroquinolin-8-amine) was obtained, revealing the catalytic activity of the complex I. The reaction proceeded under environmentally benign conditions, which liberates water as the sole byproduct. Notably, a concise synthesis of acetylcholinesterase inhibitors (AChEIs) scaffolds as potential cognition enhancers illustrated the utility of the present protocol. Interestingly, various control and deuterium-labeled experiments were performed, suggesting that the reaction proceeds via the borrowing hydrogen pathway.

Future pathways for green hydrogen: Analyzing the nexus of renewable energy consumption and hydrogen development in Chinese cities

Hydrogen energy offers a promising pathway for achieving zero-carbon urban energy consumption. This study quantitatively analyzes the patterns of hydrogen energy development and its linked to electricity consumption in China's urban areas. It investigates the spatial relationships between hydrogen energy expansion, the potential for green hydrogen production, and overall energy use. Utilizing a coupling coordination degree (CCD) model and a panel vector autoregressive (PVAR) model, the research explores the dynamic interactions between urban hydrogen energy development and the transition to renewable energy sources. In line with Chinese government policy, the study also conducts a scenario analysis of green hydrogen production by 2030, proposing a consumption strategy that balances environmental sustainability with economic growth. The key conclusions are as follows: (1) There is a spatial mismatch between the locations where hydrogen energy is being developed and where the potential for green hydrogen production is greatest. Cities with higher electricity consumption demonstrate stronger synergies in the coordinated development of hydrogen and renewable energy. (2) The development of hydrogen energy significantly accelerates the transition to renewable energy consumption in urban areas, with this impact being more substantial than that of the utilization capacity alone. (3) Hydrogen production in the Plan Scenario is significantly higher than in the Pessimistic Scenario, underscoring the critical importance of implementing renewable hydrogen projects in provinces with high production potential. Future trends in green hydrogen consumption at the provincial level indicate that addressing the challenges of efficient inter-provincial transportation of hydrogen energy remains essential.

Enhancing the ketonization efficiency of biomass through selective conversion of furanic compounds

Catalytic ketonization of biomass is an effective approach for the deoxygenation of bio-oil and the enrichment of high-purity ketone products. However, the bio-oil contains a large amount of furanic components with oxygenated side groups (e.g., furfural, furfuralcohol, etc.), which severely hinders the efficiency of the ketonization reaction. In response to this challenge, this study employed Pd-based catalysts for selective conversion of furfural into "keto-friendly" components, thereby mitigating their inhibitory effects. Initially, three morphologies of CeO2 (the main catalyst for ketonization) were selected to investigate their influence on furfural conversion. It was found that the products were mainly furfural (exceeding 86 %), with only up to approximately 13 % of "keto-friendly" products (mainly furans) detected, indicating that pure CeO2 exhibits a weak catalytic effect on the effective conversion of furfural. Compared with pure CeO2, the yield of "keto-friendly" products increased significantly when 1 wt% Pd was loaded, demonstrating the excellent catalytic performance of Pd in the effective conversion of furfural. Co-doping of Pd and Zr (5 wt%) on CeO2 further increased the "keto-friendly" products to 66 %, suggesting a synergistic effect of Pd and Zr. Mechanism analysis revealed that Pd promotes the formation of furans and benzenes by enhancing the decarbonylation of furfural and subsequent furan ring opening reactions, while the competing carbonyl hydrogenation pathway is weakened. The findings of this study will be beneficial for enhancing the biomass ketonization conversion, thereby providing valuable references for the high-value utilization of biomass.

Exclusive catalytic hydrogenation of nitrobenzene toward p-aminophenol over atomically precise Au36(SR)24 clusters.

Despite the advances in devising green methodologies for selective hydrogenation of nitrobenzene toward p-aminophenol, it is still difficult to realize p-aminophenol as the exclusive product in heterogeneous metal catalysis, as the excessive hydrogenation of nitrobenzene usually results in the aniline byproduct. Herein we report that a metal cluster containing 36 gold atoms capped by 24 thiolate ligands provides a unique pathway for nitrobenzene hydrogenation to achieve a p-aminophenol selectivity of ∼100%. The gold cluster can efficiently suppress the over-hydrogenation of amino groups via hydroxyl rearrangement with the aid of water and sequentially the proton transfer promoted by acid toward p-aminophenol. More notably, remarkable catalytic performances can be extended to clusters with similar structures such as Au28(SR)20 and Au44(SR)28, where only an atomic layer change of 2.1 Å thickness in the Au36(SR)24 cluster can tailor the proton affinity for the amino group of the key intermediate phenylhydroxylamine, thereby altering the activity while the p-aminophenol selectivity remained.

Pressure-induced generation of heterogeneous electrocatalytic metal hydride surfaces for sustainable hydrogen transfer

Metal hydrides are crucial intermediates in numerous catalytic reactions. Intensive efforts have been dedicated to constructing molecular metal hydrides, where toxic precursors and delicate mediators are usually involved. Herein, we demonstrate a facile pressure-induced methodology to generate a cost-effective heterogeneous electrocatalytic metal hydride surface for sustainable hydrogen transfer. Taking carbon dioxide (CO2) electroreduction as a model system and zinc (Zn), a well-known carbon monoxide (CO)-selective catalyst, as a model catalyst, we showcase a homogeneous-type hydrogen atom transfer process induced by heterogeneous hydride surfaces, enabling direct hydrogenation pathways traditionally considered “prohibited”. Specifically, the maximal Faradaic efficiency for formate is enhanced by ~fivefold to 83% under ambient conditions. Experimental and theoretical analyses reveal that unlike the distal hydrogenation route for CO2 to CO over pristine Zn, the Zn hydride surface enables direct hydrogenation at the carbon site of CO2 to form formate. This work provides a promising material platform for sustainable synthesis.

Contrasting Metallic (Rh0) and Carbidic (2D-Mo2C MXene) Surfaces in Olefin Hydrogenation Provides Insights on the Origin of the Pairwise Hydrogen Addition.

Kinetic studies are vital for gathering mechanistic insights into heterogeneously catalyzed hydrogenation of unsaturated organic compounds (olefins), where the Horiuti-Polanyi mechanism is ubiquitous on metal catalysts. While this mechanism envisions nonpairwise H2 addition due to the rapid scrambling of surface hydride (H*) species, a pairwise H2 addition is experimentally encountered, rationalized here based on density functional theory (DFT) simulations for the ethene (C2H4) hydrogenation catalyzed by two-dimensional (2D) MXene Mo2C(0001) surface and compared to Rh(111) surface. Results show that ethyl (C2H5*) hydrogenation is the rate-determining step (RDS) on Mo2C(0001), yet C2H5* formation is the RDS on Rh(111), which features a higher reaction rate and contribution from pairwise H2 addition compared to 2D-Mo2C(0001). This qualitatively agrees with the experimental results for propene hydrogenation with parahydrogen over 2D-Mo2C1-x MXene and Rh/TiO2. However, DFT results imply that pairwise selectivity should be negligible owing to the facile H* diffusion on both surfaces, not affected by H* nor C2H4* coverages. DFT results also rule out the Eley-Rideal mechanism appreciably contributing to pairwise addition. The measurable contribution of the pairwise hydrogenation pathway operating concurrently with the dominant nonpairwise one is proposed to be due to the dynamic site blocking at higher adsorbate coverages or another mechanism that would drastically limit the diffusion of H* adatoms.

Preparation of Ni2P with a Surface Nickel Phosphosulfide Layer by Reduction of Mixtures of Na4P2S6 and NiCl2

AbstractA series of physical mixtures of Na4P2S6 and NiCl2 (P‐NiPS(x), where x represents the P/Ni molar ratio) were employed for the preparation of Ni2P. For comparison, a sulfur‐containing Ni2P catalyst (Ni2P‐S) and a sulfur‐free Ni2P catalyst (Ni2P‐TPR) were prepared by reduction of Ni2P2S6 and a nickel phosphate precursor, respectively. The reduction of the P‐NiPS(x) precursors with P/Ni ratios above 2/3 yielded Ni2P catalysts with a distinct nickel phosphosulfide layer (NiPS(x)), and the Ni2P phase started to form at ca. 200 °C. The reduction of Ni2P2S6 to Ni2P most likely follows a disproportionation mechanism. The P3+ species in Ni2P2S6 disproportionate to PH3 and P5+ during the reduction, and PH3 further reacts with nickel and sulfur species to form Ni2P and the surface nickel phosphosulfide layer. The sulfur atoms in the nickel phosphosulfide phase were in the form of S2−. The introduction of sulfur to Ni2P favored the hydrogenation pathway of the hydrodesulfurization (HDS) of dibenzothiophene (DBT), but hardly affected the direct desulfurization (DDS) pathway and inhibited the hydrogenation of biphenyl. The DDS pathway rate constants of DBT HDS over the Ni2P‐TPR and NiPS(x) catalysts were observed to increase linearly with the increase in their surface Ni atomic concentrations.

Enhanced reductive degradation of trichloroethylene by ball milled nitridation of bimetallic Ni-ZVI: Combination effect of electron transfer and catalytic hydrogenation

The performance optimization of zerovalent iron (ZVI) based materials for reductive dechlorination is critical but remains challenging. Combining the advantages of bimetallic and heteroatomic modification may lead to a novel strategy for reductive dechlorination of chlorinated ethenes (CEs) pollution. In this study, three different types of dual-modified micron ZVI (mZVI) composite particles, namely, pre-bimetallic modified mZVI (Ni/mZVI-N), pre-nitrogen modified mZVI (N/mZVI-Ni), and simultaneously modified mZVI (Ni/N-mZVI), were prepared by adjusting the order of ball milling modification of nickel and melamine, in which ball milling mechanical-chemical interactions contributed to the generation of enriched M-N structures. In terms of combined reactivity and selectivity, Ni/N-mZVI exhibited the best performance, with trichloroethylene (TCE) dechlorination rate (kobs,TCE) and electron efficiency (εe) of 0.14 h−1 and 8.9 %, respectively, which were 10.7 and 7.5 times higher than those of mZVI. The distribution and percentage of degradation products further illustrated the reductive dechlorination of nickel-nitrogen dual-modified mZVI via both electron transfer and atomic hydrogen (H*) pathways. A series of characterization and mechanistic analyses showed that the enhancement of TCE reductive dechlorination performance could be attributed to the combined effect of Fe−N to accelerated electron transfer and Ni-N to enhance catalytic hydrogenation. In addition to decreased H2 accumulation, Ni/N-mZVI reduced leaching ions thus mitigating secondary contamination. This double-modification strategy employed to enhance the optimization of mZVI for groundwater remediation establishes a foundation for ongoing progress in the synthesis of reactive materials.

Gas-phase hydrogenation processes of cationic carbon clusters

ABSTRACT In this work, the gas-phase ion–atom collision reaction between large cationic carbon clusters and H-atoms is investigated. The carbon cluster cations (C$_{48-2*n}$$^+$, n = [0$-$8]) are produced from the photo-fragmentation processes of large PAH (dicoronylene, DC, C$_{48}$H$_{20}$) cations. The hydrogenated carbon cluster cations are efficiently formed (e.g. C$_{44/46}$H$_{9}$$^+$), and no even–odd hydrogenated mass patterns are observed. The hydrogenation behaviour and hydrogenation rate for these carbon cluster cations are the same. With theoretical calculations, the formation and bending processes of carbon cluster cations, the structure of these newly formed hydrogenated carbon cluster cations, and the bonding energies for the hydrogenation pathways are investigated. During the formation process of carbon clusters, the zigzagged edges gradually increase, and the planar configuration tends towards a bent and folded molecular configuration, i.e. from graphene to fullerene structures. The bending process with higher exothermic energies provides a reasonable explanation for the formation of the ‘magic numbers’ (e.g. C-atoms = 44) carbon clusters and their greater stability. The exothermic energy for each hydrogenation reaction pathway is relatively high; consequently, the forms and the hydrogenated states of carbon clusters are complex. The hydrogenation ability of edge carbon sites is higher than that of internal carbon sites; after bending and folding, the hydrogenation ability of these originally internal carbon sites becomes higher due to structural caged. As a result, under the co-evolution interstellar chemistry network, the (hydrogenation) states and forms of carbon compounds are complicated and diverse in the ISM.

Effect of copper cluster on reaction pathways of carbon dioxide hydrogenation on magnesium hydride surface

Understanding the reaction mechanism of CO2 hydrogenation to produce value-added chemicals is essential for the rational design of catalysts to improve reaction activity and product selectivity. In this work, the first-principles calculations based on density functional theory were employed to study the effect of copper cluster on product selectivity in CO2 hydrogenation utilizing magnesium hydride as hydrogen source. The results show that on pristine MgH2 (0 0 1), CO2 molecule adsorbs on the surface with an O atom close to Mg atom, and the hydrogenation reaction follows formate pathway to yield CH3OH with an energy barrier only 1.09 eV for the rate-limiting step; however, the production of the most accessible C2-based product (CH2OH)2 needs to overcome an energy barrier up to 1.94 eV. On MgH2 (0 0 1) with Cu7 cluster, the C atom of CO2 molecule can strongly adsorb on a Cu atom of Cu7 cluster, and the hydrogenation more likely proceeds through reverse water-gas shift pathway, in which it is easy to generate C2 product C2H4 by the coupling of intermediate H2C*, with an energy barrier only 1.53 eV for the rate-limiting step. The findings utilizing transition metal cluster to change the reaction pathway and product selectivity of CO2 hydrogenation on magnesium hydride can provide novel perspectives for the design of catalysts.

Selective reduction of CO2 to ethanol over Si/Cu(1 1 1) surface: An insights from the first-principles calculations

In this study, reaction mechanism of the electrocatalytic reduction of CO2 to C2H5OH over the Si/Cu(111) surface were systematically investigated by using the first-principles calculations. The results show that the introduction of oxyphilic Si atom into Si/Cu(111) surface forms the Siδ+-(Cu6)δ- configuration, which can effectively adsorb CO2 with a considerable adsorption energy. The adsorbed CO2 could be reduced to CO by a unique dissociation adsorption process induced by the aerobic Si center. Compared to the original Cu(111) surface, the introduction of a Si atom is thermodynamically and kinetically beneficial for the dimerization of CO. The presence of an oxyphilic Si atom on the Cu(111) surface can effectively improve the selectivity for ethanol products by forming Si-O bonds on the hydrogenation pathway.

Electrocatalytic Transfer Hydrogenation of 1‐Octene with [(tBuPCP)Ir(H)(Cl)] and Water

AbstractElectrocatalytic hydrogenation of 1‐octene as non‐activated model substrate with neutral water as H‐donor is reported, using [(tBuPCP)Ir(H)(Cl)] (1) as the catalyst, to form octane with high faradaic efficiency (FE) of 96 % and a kobs of 87 s−1. Cyclic voltammetry with 1 revealed that two subsequent reductions trigger the elimination of Cl− and afford the highly reactive anionic Ir(I) hydride complex [(tBuPCP)Ir(H)]− (2), a previously merely proposed intermediate for which we now report first experimental data by mass spectrometry. In absence of alkene, the stoichiometric electrolysis of 1 in THF with water selectively affords the Ir(III) dihydride complex [(tBuPCP)Ir(H)2] (3) in 88 % FE from the reaction of 2 with H2O. Complex 3 then hydrogenates the alkene in classical fashion. The presented electro‐hydrogenation works with extremely high FE, because the iridium hydrides are water stable, which prevents H2 formation. Even in strongly alkaline conditions (Bu4NOH added), the electro‐hydrogenation of 1‐octene with 1 also proceeds cleanly (89 % FE), suggesting a highly robust process that may rely on H2O activation, reminiscent to transfer hydrogenation pathways, instead of classical H+ reduction. DFT calculations confirmed oxidative addition of H2O as a key step in this context.

Electrocatalytic Transfer Hydrogenation of 1-Octene with [(tBuPCP)Ir(H)(Cl)] and Water.

Electrocatalytic hydrogenation of 1-octene as non-activated model substrate with neutral water as H-donor is reported, using [(tBuPCP)Ir(H)(Cl)] (1) as the catalyst, to form octane with high faradaic efficiency (FE) of 96 % and a kobs of 87 s-1. Cyclic voltammetry with 1 revealed that two subsequent reductions trigger the elimination of Cl- and afford the highly reactive anionic Ir(I) hydride complex [(tBuPCP)Ir(H)]- (2), a previously merely proposed intermediate for which we now report first experimental data by mass spectrometry. In absence of alkene, the stoichiometric electrolysis of 1 in THF with water selectively affords the Ir(III) dihydride complex [(tBuPCP)Ir(H)2] (3) in 88 % FE from the reaction of 2 with H2O. Complex 3 then hydrogenates the alkene in classical fashion. The presented electro-hydrogenation works with extremely high FE, because the iridium hydrides are water stable, which prevents H2 formation. Even in strongly alkaline conditions (Bu4NOH added), the electro-hydrogenation of 1-octene with 1 also proceeds cleanly (89 % FE), suggesting a highly robust process that may rely on H2O activation, reminiscent to transfer hydrogenation pathways, instead of classical H+ reduction. DFT calculations confirmed oxidative addition of H2O as a key step in this context.