Molecular Hydrogen, a Neglected Key Driver of Soil Biogeochemical Processes.

The atmosphere of the early Earth is hypothesized to have been rich in reducing gases such as hydrogen (H2). H2 has been proposed as the first electron donor leading to ATP synthesis due to its ubiquity throughout the biosphere as well as its ability to easily diffuse through microbial cells and its low activation energy requirement. Even today, hydrogenase enzymes enabling the production and oxidation of H2 are found in thousands of genomes spanning the three domains of life across aquatic, terrestrial, and even host-associated ecosystems. Even though H2 has already been proposed as a universal growth and maintenance energy source, its potential contribution as a driver of biogeochemical cycles has received little attention. Here, we bridge this knowledge gap by providing an overview of the classification, distribution, and physiological role of hydrogenases. Distribution of these enzymes in various microbial functional groups and recent experimental evidence are finally integrated to support the hypothesis that H2-oxidizing microbes are keystone species driving C cycling along O2 concentration gradients found in H2-rich soil ecosystems. In conclusion, we suggest focusing on the metabolic flexibility of H2-oxidizing microbes by combining community-level and individual-level approaches aiming to decipher the impact of H2 on C cycling and the C-cycling potential of H2-oxidizing microbes, via both culture-dependent and culture-independent methods, to give us more insight into the role of H2 as a driver of biogeochemical processes.

Interprotein Electron Transfer between FeS-Protein Nanowires and Oxygen-Tolerant NiFe Hydrogenase.

Self-assembled redox protein nanowires have been exploited as efficient electron shuttles for an oxygen-tolerant hydrogenase. An intra/inter-protein electron transfer chain has been achieved between the iron-sulfur centers of rubredoxin and the FeS cluster of [NiFe] hydrogenases. [NiFe] Hydrogenases entrapped in the intricated matrix of metalloprotein nanowires achieve a stable, mediated bioelectrocatalytic oxidation of H2 at low-overpotential.

Carbon-Nanotube-Supported Bio-Inspired Nickel Catalyst and Its Integration in Hybrid Hydrogen/Air Fuel Cells.

A biomimetic nickel bis-diphosphine complex incorporating the amino acid arginine in the outer coordination sphere was immobilized on modified carbon nanotubes (CNTs) through electrostatic interactions. The functionalized redox nanomaterial exhibits reversible electrocatalytic activity for the H2 /2 H+ interconversion from pH 0 to 9, with catalytic preference for H2 oxidation at all pH values. The high activity of the complex over a wide pH range allows us to integrate this bio-inspired nanomaterial either in an enzymatic fuel cell together with a multicopper oxidase at the cathode, or in a proton exchange membrane fuel cell (PEMFC) using Pt/C at the cathode. The Ni-based PEMFC reaches 14 mW cm-2 , only six-times-less as compared to full-Pt conventional PEMFC. The Pt-free enzyme-based fuel cell delivers ≈2 mW cm-2 , a new efficiency record for a hydrogen biofuel cell with base metal catalysts.

Arginine-containing ligands enhance H2 oxidation catalyst performance.

Hydrogenase enzymes use Ni and Fe to oxidize H2 at high turnover frequencies (TOF) (up to 10,000 s(-1)) and low overpotentials (<100 mV). In comparison, the fastest reported synthetic electrocatalyst, [Ni(II)(P(Cy)2N(tBu)2)2](2+), oxidizes H2 at 60 s(-1) in MeCN under 1 atm H2 with an unoptimized overpotential of ca. 500 mV using triethylamine as a base. Here we show that a structured outer coordination sphere in a Ni electrocatalyst enhances H2 oxidation activity: [Ni(II)(P(Cy)2N(Arg)2)2](8+) (Arg=arginine) has a TOF of 210 s(-1) in water with high energy efficiency (180 mV overpotential) under 1 atm H2 , and 144,000 s(-1) (460 mV overpotential) under 133 atm H2. The complex is active from pH 0-14 and is faster at low pH, the most relevant condition for fuel cells. The arginine substituents increase TOF and may engage in an intramolecular guanidinium interaction that assists in H2 activation, while the COOH groups facilitate rapid proton movement. These results emphasize the critical role of features beyond the active site in achieving fast, efficient catalysis.

Insight into the high-temperature oxidation kinetics of acetylene: A first-principles molecular dynamics study.

The study on high-temperature oxidation kinetics and kinetic modeling of acetylene (C2H2) has significant importance for its engineering applications. In this paper, the first-principles molecular dynamics method is used to simulate the C2H2 oxidation under high temperatures for the first time. Our results show that there are 38 intermediates and 225 elementary reactions in the process of C2H2 oxidation. The formation mechanisms of "prompt" CO2, as well as gas pollutants CHOCHO and HCOOH are revealed in depth. Four intermediates, CHCHO, CHOCO, CHOCHO and HCOOH, which have significant controversy in current kinetic models, are verified. And a new intermediate, CHOCO2, is discovered. Meanwhile, our simulation also shows that radicals, such as HO2, OH, O, etc. play a key role in promoting the oxidation of intermediates in the early stage of C2H2 oxidation. Combined with quantum chemical calculations, a detailed chemical kinetic model of C2H2/air (FP-C2H2) is built and verified by simulating ignition delay time, species concentration in the flow reactor and premixed laminar flame speed. Our studies provide novel insight for understanding the complex chemical reaction kinetics, and environmental and human health threats from air pollutant formation during C2H2 combustion.

Theoretical Investigation of the Electrochemical Oxidation of H2 and CO Fuels on a Ruddlesden-Popper SrLaFeO4-δ Anode.

The electrochemical oxidation of H2 and CO fuels have been investigated on the Ruddlesden-Popper layered perovskite SrLaFeO4-δ (SLF) under anodic solid oxide fuel cell conditions using periodic density functional theory and microkinetic modeling techniques. Two distinct FeO2-plane-terminated surface models differing in terms of the underlying rock salt layer (SrO or LaO) are used to identify the active site and limiting factors for the electro-oxidation of H2, CO, and syngas fuels. Microkinetic modeling predicted an order of magnitude higher turnover frequency for the electro-oxidation of H2 compared to CO for SLF at short-circuit conditions. The surface model with an underlying SrO layer was found to be more active with respect to H2 oxidation than the LaO-based surface model. At an operating voltage of less than 0.7 V, surface H2O/CO2 formation was found to be the key rate-limiting step, and the surface H2O/CO2 desorption was the key charge transfer step. In contrast, the bulk oxygen migration process was found to affect the overall rate at high cell voltage conditions above 0.9 V. In the presence of syngas fuel, the overall electrochemical activity is derived mainly from H2 electro-oxidation and CO2 is chemically shifted to CO via the reverse water-gas shift reaction. Substitutional doping of a surface Fe atom with Co, Ni, and Mn revealed that the H2 electro-oxidation activity of FeO2-plane terminated anodes with an underlying LaO rock salt layer can be improved with dopant introduction, with Co yielding a three orders of magnitude higher activity relative to the undoped LaO surface model. Constrained ab initio thermodynamic analysis furthermore suggested that the SLF anodes are resistant toward sulfur poisoning both in the presence and absence of dopants. Our findings reflect the role of various elements in controlling the fuel oxidation activity of SLF anodes that could aid the development of new Ruddlesden-Popper phase materials for fuel cell applications.

Selective formate production from H2 and CO2 using encapsulated whole-cells under mild reaction conditions.

Biocatalytic CO2 reduction into formate is a crucial strategy for developing clean energy because formate is considered as one of the promising hydrogen storage materials for achieving net-zero carbon emissions. Here, we developed an efficient biocatalytic system to produce formate selectively by coupling two enzymatic activities of H2 oxidation and CO2 reduction using encapsulated bacterial cells of Citrobacter sp. S-77. The encapsulated whole-cell catalyst was made by living cells depositing into polyvinyl alcohol and gellan gum cross-linked by calcium ions to form hydrogel beads. Formate production using encapsulated cells was carried out under the resting state conditions in the gas mixture of H2/CO2 (70:30, v/v%). The whole-cell biocatalyst showed highly efficient and selective catalytic production of formate, reaching the specific rate of formate production of 110 mmol L-1· gprotein-1·h-1 at 30 °C, pH 7.0, and 0.1 MPa. The encapsulated cells can be reused at least 8 times while keeping their high catalytic activities for formate production under mild reaction conditions.

Electroshock synthesis of a bifunctional nonprecious multi-element alloy for alkaline hydrogen oxidation and evolution.

The design and production of active, durable, and nonprecious electrocatalysts toward alkaline hydrogen oxidation and evolution reactions (HOR/HER) are extremely appealing for the implementation of hydrogen economy, but remain challenging. Here, we report a facile electric shock synthesis of an efficient, stable, and inexpensive NiCoCuMoW multi-element alloy on Ni foam (NiCoCuMoW) as a bifunctional electrocatalyst for both HOR and HER. For the HOR, the current density of NiCoCuMoW could reach ∼11.2 mA cm-2 when the overpotential is 100 mV, higher than that for commercial Pt/C (∼7.2 mA cm-2) and control alloy samples with less elements, along with superior CO tolerance. Moreover, for the HER, the overpotential at 10 mA cm-2 for NiCoCuMoW is only 21 mV, along with a Tafel slope of low to 63.7 mV dec-1, rivaling the commercial Pt/C as well (35 mV and 109.7 mV dec-1). Density functional theory calculations indicate that alloying Ni, Co, Cu, Mo, and W can tune the electronic structure of individual metals and provide multiple active sites to optimize the hydrogen and hydroxyl intermediates adsorption, collaboratively resulting in enhanced electrocatalytic activity.

QM/MM study of the binding of H2 to MoCu CO dehydrogenase: development and applications of improved H2 van der Waals parameters.

The MoCu CO dehydrogenase enzyme not only transforms CO into CO2 but it can also oxidise H2. Even if its hydrogenase activity has been known for decades, a debate is ongoing on the most plausible mode for the binding of H2 to the enzyme active site and the hydrogen oxidation mechanism. In the present work, we provide a new perspective on the MoCu-CODH hydrogenase activity by improving the in silico description of the enzyme. Energy refinement-by means of the BigQM approach-was performed on the intermediates involved in the dihydrogen oxidation catalysis reported in our previously published work (Rovaletti, et al. "Theoretical Insights into the Aerobic Hydrogenase Activity of Molybdenum-Copper CO Dehydrogenase." Inorganics 7 (2019) 135). A suboptimal description of the H2-HN(backbone) interaction was observed when the van der Waals parameters described in previous literature for H2 were employed. Therefore, a new set of van der Waals parameters is developed here in order to better describe the hydrogen-backbone interaction. They give rise to improved binding modes of H2 in the active site of MoCu CO dehydrogenase. Implications of the resulting outcomes for a better understanding of hydrogen oxidation catalysis mechanisms are proposed and discussed.

Excellent Electrochemical Performance of La0.3Sr0.7Fe0.9Ti0.1O3-δ as a Symmetric Electrode for Solid Oxide Cells.

Solid oxide cells (SOCs) can switch between fuel cell and electrolysis cell modes, which alleviate environmental and energy problems. In this study, the La0.3Sr0.7Fe0.9Ti0.1O3-δ (LSFTi 91) perovskite is innovatively used as a symmetric electrode for solid oxide electrolysis cells (SOECs) and solid oxide fuel cells (SOFCs). LSFTi 91 exhibits a pure perovskite phase in both oxidizing and reducing atmospheres, and the maximum conductivity in air and 5% H2/Ar is 150 and 1.1 S cm-1, respectively, which meets the requirement of the symmetric electrode. The polarization resistance (Rp) at 1.5 V is as low as 0.09 Ω cm2 in the SOEC mode due to the excellent CO2 adsorption capacity. The current density can reach 1.9 A cm-2 at 1.5 V and 800 °C, which is the highest electrolytic performance in the reported single-phase electrodes. LSFTi 91 also exhibits eminent oxygen reduction reaction and hydrogen oxidation reaction (ORR and HOR) activities, with Rp of 0.022 and 0.15 Ω cm2 in air and wet H2, respectively. The peak power density of SOFC could reach 847 mW cm-2 at 800 °C. In addition, good reversibility is confirmed in the cyclic operation of SOFC and SOEC.

The Extended C-Terminal α-Helix of the HypC Chaperone Restricts Recognition of Large Subunit Precursors by the Hyp-Scaffold Machinery during [NiFe]-Hydrogenase Maturation in Escherichia coli.

Members of the HypC protein family are chaperone-like proteins that play a central role in the maturation of [NiFe]-hydrogenases (Hyd). Escherichia coli has a second copy of HypC, called HybG, and, as a component of the HypDEF maturation scaffold, these proteins help synthesize the NiFe-cofactor and guide the scaffold to its designated hydrogenase large subunit precursor. HypC is required to synthesize active Hyd-1 and Hyd-3, while HybG facilitates Hyd-2 and Hyd-1 synthesis. To identify determinants on HypC that allow it to discriminate against Hyd-2, we made amino acid exchanges in 3 variable regions, termed VR1, VR2, and VR3, of HypC, that make it more similar to HybG. Region VR3 includes a HypC-specific C-terminal α-helical extension, and this proved particularly important in preventing the maturation of Hyd-2 by HypC. Truncation of this extension on HypC increased Hyd-2 activity in the absence of HybG, while retaining maturation of Hyd-3 and Hyd-1. Combining this truncation with amino acid exchanges in VR1 and VR2 of HypC negatively affected the synthesis of active Hyd-1. The C-terminus of E. coli HypC is thus a key determinant in hindering Hyd-2 maturation, while VR1 and VR2 appear more important for Hyd-1 matu-ration.

Performance of different Sporomusa species for the microbial electrosynthesis of acetate from carbon dioxide.

Sporomusa ovata DSM-2662 produces high rate of acetate during microbial electrosynthesis (MES) by reducing CO2 with electrons coming from a cathode. Here, we investigated other Sporomusa for MES with cathode potential set at -690mVvsSHE to establish if this capacity is conserved among this genus and to identify more performant strains. S. ovata DSM-2663 produced acetate 1.8-fold faster than S. ovata DSM-2662. On the contrary, S. ovata DSM-3300 was 2.7-fold slower whereas Sporomusa aerivorans had no MES activity. These results indicate that MES performance varies among Sporomusa. During MES, electron transfer from cathode to microbes often occurs via H2. To establish if efficient coupling between H2 oxidation and CO2 reduction may explain why specific acetogens are more productive MES catalysts, the metabolisms of the investigated Sporomusa were characterized under H2:CO2. Results suggest that other phenotypic traits besides the capacity to oxidize H2 efficiently are involved.