Proton Source Research Articles

Metal-Free Homogeneous O2 Reduction by an Iminium-Based Electrocatalyst.

The oxygen reduction reaction (ORR) is important for alternative energy and industrial oxidation processes. Herein, an iminium-based organoelectrocatalyst (im+) for the ORR with trifluoroacetic acid as a proton source in acetonitrile solution under both electrochemical and spectrochemical conditions using decamethylferrocene as a chemical reductant is reported. Under spectrochemical conditions, H2O2 is the primary reaction product, while under electrochemical conditions H2O is produced. This difference in selectivity is attributed to the interception of the free superoxide intermediate under electrochemical conditions by the reduced catalyst, accessing an alternate inner-sphere pathway.

Three-dimensional particle-in-cell simulations of laser-driven multiradiation sources based on double-layer targets.

Double-layer targets (DLTs), made of a low-density foam on top of a solid substrate, can efficiently convert the energy of a high-intensity laser to provide sources of photons and protons. We investigate a 30-fs pulse with a peak intensity of I∼8.7×10^{20}W/cm^{2} and a peak power of ∼120 TW interacting with a DLT using three-dimensional (3D) particle-in-cell simulations. We focus on providing quantitative results in full 3D geometry on the foam thickness dependence; on the competition between two photon-generating processes in DLTs, i.e., nonlinear inverse Compton scattering (NICS) and bremsstrahlung (BS); and on the acceleration of protons via enhanced target-normal sheath acceleration. We discuss conversion efficiency, average energy, and angular distributions of such multiradiation sources. We find that NICS can prevail over BS if the DLT's substrate is thin enough (∼µm) and that the optimal foam thickness that maximizes the conversion efficiency in NICS and BS photons and the proton cutoff energy, among those considered, is the same (15µm). These results show that DLTs constitute an excellent tool for developing relatively compact and optimized laser-driven multicomponent radiation sources.

Electrochemical CO2 Reduction by Urea Hangman Mn Terpyridine species.

Based on our previous study in chemical subtleties of the proton tunneling distance for metal hydride formation (PTD-MH) to regulate the selectivity of CO2 reduction reaction (CO2RR), we have developed a family of Mn terpyridine derivatives, in which urea groups functions as multipoint hydrogen-bonding hangman to accelerate the reaction rate. We found that such changes to the second coordination sphere significantly increased the turnover frequency (TOF) for CO2 reduction to ca. 360 with this family of molecular catalysts while maintaining high selectivity (ca. 100 %±3) for CO even in the presence of a large amount of phenol as proton source. Notably, the compounds studied in this manuscript all exhibit large value for as that achieved by Fe porphyrins derivates, while saving up to 0.55 V in overpotential with respect to the latter.

Diiron azadithiolate models with bulky bridgehead moiety: Synthesis, structure and electrochemistry

To further explore the function of azadithiolate (ADT) bridges in diiron complexes and to develop new biomimics for the active site of [FeFe]-H2ases, here a new model complex [Fe2{(μ-SCH2)2NCHPh2}(CO)6] (1), featuring a bulky bridgehead (CHPh2) was prepared by condensation reaction of [Fe2(μ-SCH2OH)2(CO)6] and NH2CHPh2. The corresponding monophosphine-substituted diiron azadithiolate complexes, [Fe2{(μ-SCH2)2NCHPh2}(CO)5 L] (2–7) [L = PPh3, PPh2(2-C5H4N), PPh2(C6H11), P(C6H4–4-CH3)3, P(C6H4–4–OCH3)3, P(2-C4H3O)3], were prepared via the one-pot method that involves [Fe2(μ-SCH2OH)2(CO)6], phosphine ligand and NH2CHPh2. The diphosphine-substituted complexes, [Fe2{(μ-SCH2)2NCHPh2}(CO)5(κ1-dppm)] [dppm = CH2(PPh2)2] (8), [Fe2{(μ-SCH2)2NCHPh2} (CO)4{(κ2-Ph2P)2NCH2C6H5}] (9), [Fe2{(μ-SCH2)2NCHPh2}(CO)4(μ-dppm)] (10) and [Fe2{(μ-SCH2)2NCHPh2}(CO)4{(μ-Ph2P)2NCH2Ph}] (11) were synthesized using either Me3NO-assisted oxidative decarbonylation reaction or thermal reaction. All the new complexes were fully structurally characterized by elemental analysis, spectroscopies, and particularly for 2–10 by X-ray crystallography. Furthermore, the electrochemical and electrocatalytic properties of these model complexes were investigated by cyclic voltammetry, demonstrating their ability to catalyze the reduction of protons to produce H2 when acetic acid was used as the proton source.

Artificial Photosynthesis for Regioselective Reduction of NAD(P)+ to NAD(P)H Using Water as an Electron and Proton Source.

In photosynthesis, four electrons and four protons taken from water in photosystem II (PSII) are used to reduce NAD(P)+ to produce NAD(P)H in photosystem I (PSI), which is the most important reductant to reduce CO2. Despite extensive efforts to mimic photosynthesis, artificial photosynthesis to produce NAD(P)H using water electron and proton sources has yet to be achieved. Herein, we report the photocatalytic reduction of NAD(P)+ to NAD(P)H and its analogues in a molecular model of PSI, which is combined with water oxidation in a molecular model of PSII. Photoirradiation of a toluene/trifluoroethanol (TFE)/borate buffer aqueous solution of hydroquinone derivatives (X-QH2), 9-mesityl-10-methylacridinium ion, cobaloxime, and NAD(P)+ (PSI model) resulted in the quantitative and regioselective formation of NAD(P)H and p-benzoquinone derivatives (X-Q). X-Q was reduced to X-QH2, accompanied by the oxidation of water to dioxygen under the photoirradiation of a toluene/TFE/borate buffer aqueous solution of [(N4Py)FeII]2+ (PSII model). The PSI and PSII models were combined using two glass membranes and two liquid membranes to produce NAD(P)H using water as an electron and proton source with the turnover number (TON) of 54. To the best of our knowledge, this is the first time to achieve the stoichiometry of photosynthesis, photocatalytic reduction of NAD(P)+ by water to produce NAD(P)H and O2.

Electrocatalytic hydrogen evolution by cobalt(Ⅲ) triphenyl corrole bearing different number of trifluoromethyl groups

Hydrogen production from electrolyzing water is known as the most promising hydrogen production method. To further understand the effect of steric hindrance and electron-withdrawing groups on catalysts, four cobalt triphenyl corroles bearing different number of ortho-trifluoromethyls (1, 2, 3, 4) had been synthesized and used as hydrogen evolution electrocatalysts. These cobalt corroles showed effective electrocatalytic hydrogen evolution activity in organic medium and neutral aqueous medium, with turnover frequency ranging from 100 s−1 to 220 s−1 using 32 equivalents of trifluoroacetic acid proton source in DMF. The electrocatalytic HER goes via competitive ECEC or EECC pathway depending on the used proton source. The electrocatalytic HER activity varies obviously with the number of the peripheral ortho- groups. This work is helpful for the design of new metal corrole HER electrocatalyst.

Aqueous Electrocatalytic Reduction as a Low‐Carbon and Green Route for Chemical Synthesis and Environmental Remediation

AbstractThe green electricity‐driven electrocatalytic reduction of organic compounds in aqueous solution has merged as a sustainable and green platform for organic electrosynthesis, upcycling of chemical waste, and environmental remediation. Compared with the thermocatalytic hydrogenation process, the electrocatalytic reduction of organic compounds uses water as a proton source, which enables its operation at ambient conditions with simplified reaction schemes and significantly reduces operation cost and energy consumption. Most studies have demonstrated the development of electrocatalysts to boost the current efficiency, conversion, and product selectivity of the electrocatalytic reduction processes. Still, little attention has been paid to the mechanism (e. g., electron/proton transfer route) and related energetics behind the electrocatalytic reduction process. This Concept overviews the recent development of the electrocatalytic reduction systems for environmental remediation, pollutant upcycling, and valorization of biomass‐derived chemicals. This Concept highlights the underlying mechanisms and aims to provide instructive guidance on designing efficient and selective electrocatalytic systems.

Exploring the influence of interfacial solvation on electrochemical CO2 reduction using plasmon‐enhanced vibrational sum frequency generation spectroscopy

AbstractAlthough interfacial solvation plays an important role in determining carbon dioxide reduction (CO2R) kinetics, present understanding of the potential dependent properties of the electrochemical double layer under conditions relevant for CO2R remains limited. This article summarizes the development and recent applications of plasmon‐enhanced vibrational sum frequency generation (VSFG) spectroscopy to study the effects of cation hydration and interfacial solvation on CO2R using CO as a vibrational Stark reporter. Results show that electrolyte cations retain their entire solvation shell upon adsorption to inactive sites, while active sites retain only a single water layer between the gold surface and the cation. Measurements also show that the total interfacial electric field can be separated into two contributions: one from the electrochemical double layer (Stern field) and another from the polar solvation environment (Onsager field). Surprisingly, correlating VSFG spectra with reaction kinetics reveals that it is the solvation‐mediated Onsager field that governs the chemical reactivity at the electrode/electrolyte interface. Measuring the interfacial water spectra during electrocatalysis also provides evidence for the proton source during H2 evolution, which competes with CO2R in aqueous electrolyte. These findings highlight the importance of directly probing cation hydration and interfacial solvation, which mediates reaction kinetics at electrochemical interfaces.

Transverse emittance growth of proton sources from laser-irradiated sub-μm-thin planar targets.

Proton bunches with maximum energies between 12 and 22 MeV were emitted from submicrometer-thin plastic foils upon irradiation by laser pulses with peak intensity of 4×10^{20}W/cm^{2}. The images of the protons by a magnetic quadrupole doublet on a screen remained consistently larger by a factor of 10 compared to expectations drawn from the ultralow transverse emittance values reported for thick foil targets. Analytic estimates and particle-in-cell simulations attribute this drastically increased emittance to formerly excluded Coulomb collisions between charged particles. The presence of carbon ions and significant transparency likely play a decisive role. This observation is highly relevant because such thin, partially transparent foils are considered ideal for optimizing maximum proton energies.

Electrolytic Hydrogen Release from Hydrogen Boride Sheets.

Solid-state hydrogen storage materials are safe and lightweight hydrogen carriers. Among the various solid-state hydrogen carriers, hydrogen boride (HB) sheets possess a high gravimetric hydrogen capacity (8.5 wt%). However, heating at high temperatures and/or strong ultraviolet illumination is required to release hydrogen (H2) from HB sheets. In this study, the electrochemical H2 release from HB sheets using a dispersion system in an organic solvent without other proton sources is investigated. H2 molecules are released from the HB sheets under the application of a cathodic potential. The Faradaic efficiency for H2 release from HB sheets reached >90%, and the onset potential for H2 release is -0.445V versus Ag/Ag+, which is more positive than those from other proton sources, such as water or formic acid, under the same electrochemical conditions. The total electrochemically released H2 in a long-time experiment reached ≈100% of the hydrogen capacity of HB sheets. The H2 release from HB sheets is driven by a small bias; thus, they can be applied as safe and lightweight hydrogen carriers with economical hydrogen release properties.

Effect of Variable Amine Pendants in the Secondary Coordination Sphere of Manganese Bipyridine Complexes on the Electrochemical CO2 Reduction

AbstractThe increasing concentration of CO2 in the atmosphere and its impact on the climate are matters of significant concern. Extensive research is being conducted on molecular catalysts to electrochemically reduce CO2 into valuable products to disrupt the unidirectional carbon flow. This study compares two manganese bipyridine catalysts, tailored with four or two benzylic diethylamine groups in the secondary coordination sphere. Either of these amine‐bearing scaffolds positioned close to the Mn center serves as effective proton relays to facilitate the formation of the corresponding Mn hydride intermediate. Alongside competitive H2 evolution, the reaction of this crucial intermediate with CO2 leads to formate. Our findings underscore the pronounced influence of external Brønsted acids on product selectivity. Notably, when employing the catalyst bearing four amine groups, the HCOO−/H2 ratio varies from 81 : 3 with 1.0 M iPrOH to 16 : 64 with 1.0 M PhOH, while the Mn complex adorned with two amine pendant groups consistently favors HCOO−, irrespective of the utilized proton sources. Infrared spectroelectrochemistry and density‐functional theory calculations unveil distinct disparities in the reactivity of the Mn hydrides toward CO2 due to the change of ligand bulkiness in the two cases. This work substantiates the importance of modulating spatial accessibility while modifying the second sphere encompassing molecular catalysts.

Nanoarchitectonics with a Membrane‐Embedded Electron Shuttle Mimics the Bioenergy Anabolism of Mitochondria

AbstractEnhanced bioenergy anabolism through transmembrane redox reactions in artificial systems remains a great challenge. Here, we explore synthetic electron shuttle to activate transmembrane chemo‐enzymatic cascade reactions in a mitochondria‐like nanoarchitecture for augmenting bioenergy anabolism. In this nanoarchitecture, a dendritic mesoporous silica microparticle as inner compartment possesses higher load capacity of NADH as proton source and allows faster mass transfer. In addition, the outer compartment ATP synthase‐reconstituted proteoliposomes. Like natural enzymes in the mitochondrion respiratory chain, a small synthetic electron shuttle embedded in the lipid bilayer facilely mediates transmembrane redox reactions to convert NADH into NAD+ and a proton. These facilitate an enhanced outward proton gradient to drive ATP synthase to rotate for catalytic ATP synthesis with improved performance in a sustainable manner. This work opens a new avenue to achieve enhanced bioenergy anabolism by utilizing a synthetic electron shuttle and tuning inner nanostructures, holding great promise in wide‐range ATP‐powered bioapplications.

Nanoarchitectonics with a Membrane-Embedded Electron Shuttle Mimics the Bioenergy Anabolism of Mitochondria.

Enhanced bioenergy anabolism through transmembrane redox reactions in artificial systems remains a great challenge. Here, we explore synthetic electron shuttle to activate transmembrane chemo-enzymatic cascade reactions in a mitochondria-like nanoarchitecture for augmenting bioenergy anabolism. In this nanoarchitecture, a dendritic mesoporous silica microparticle as inner compartment possesses higher load capacity of NADH as proton source and allows faster mass transfer. In addition, the outer compartment ATP synthase-reconstituted proteoliposomes. Like natural enzymes in the mitochondrion respiratory chain, a small synthetic electron shuttle embedded in the lipid bilayer facilely mediates transmembrane redox reactions to convert NADH into NAD+ and a proton. These facilitate an enhanced outward proton gradient to drive ATP synthase to rotate for catalytic ATP synthesis with improved performance in a sustainable manner. This work opens a new avenue to achieve enhanced bioenergy anabolism by utilizing a synthetic electron shuttle and tuning inner nanostructures, holding great promise in wide-range ATP-powered bioapplications.

Inhibition of hydrogen evolution in proton battery by sulfamic acid-caprolactam electrolyte and its electrochemical study

Proton batteries are expected to be used in large-scale energy storage systems in the future because of their reliability, safety, non-toxicity, and low cost. However, the hydrogen evolution reaction in the electrolyte of a proton battery limits the development of a high-voltage proton battery, and it is difficult to study the anode materials with lower charge and discharge potential. In this study, a novel sulfamic acid-caprolactam based electrolytes for inhibiting hydrogen evolution in the proton batteries was investigated. Aminosulfonic acid was used as a proton source in the proton batteries for the first time. In addition, caprolactam cosolvent with double hydrogen bond site was added to the electrolyte to help H3O+ de-solvent into H+, which effectively inhibited the hydrogen evolution behavior in the electrolyte of proton battery. The MoO3 electrode showed good cycling stability in the SA-H2O-CPL electrolyte. After 300 cycles, the capacity retention rate was 83.3%, and the average CE value was 99.7%. After adding caprolactam to the electrolyte, the hydrogen evolution potential is reduced to -1.7 V, and the electrochemical stability window of the electrolyte is greatly widened, which will help to develop anode materials with lower redox potential and be of great significance to the realization of high voltage proton batteries.

Hydrogen evolution driven by heteroatoms of bidentate N-heterocyclic ligands in iron(II) complexes.

While Pt is considered the best catalyst for the electrocatalytic hydrogen evolution reaction (HER), it is evident that non-noble metal alternatives must be explored. In this regard, it is well known that the binding sites for non-noble metals play a pivotal role in facilitating efficient catalysis. Herein, we studied Fe(II) complexes with bidentate 2-(2'-pyridyl)benzoxazole (LO), 2-(2'-pyridyl)benzthiazole (LS), 2-(2'-pyridyl)benzimidazole (LNH), and 2-2'-bipyridyl (Lpy) ligands - by adding trifluoroacetic acid (TFA) to their acetonitrile solution - in order to examine how their reactivity towards protons under reductive conditions could be impacted by the non-coordinating heteroatoms (S, O, N, or none). By applying this ligand series, we found that the reduction potentials relevant for HER correlate with ligand basicity in the presence of TFA. Moreover, DFT calculations underlined the importance of charge distribution in the ligand-based LUMO and LUMO+1 orbitals of the complexes, dependent on the heterocycle. Kinetic studies and controlled potential electrolysis - using TFA as a proton source - revealed HER activities for the complexes with LNH, LO, and LS of kobs = 0.03, 1.1, and 10.8 s-1 at overpotentials of 0.81, 0.76, and 0.79 V, respectively, and pointed towards a correlation between the kinetics of the reaction and the non-coordinating heteroatoms of the ligands. In particular, the activity was associated with the [Fe(LS/O/NH)2(S)2]2+ form (S = solvent or substrate molecule), and the rate-determining step involved the formation of [Fe(H-H)]+, during the weakening of Fe-H and CF3CO2-H bonds, according to the experimental and DFT results.

Catalytic reduction of oxygen to water by non-heme iron complexes: exploring the effect of the secondary coordination sphere proton exchanging site.

In this study, we prepared non-heme FeIII complexes (1, 2, and 3) of an N4 donor set of ligands (H2L, Me2L, and BPh2L). 1 is supported by a monoanionic bispyridine-dioxime ligand (HL). In 2 and 3, the primary coordination sphere of Fe remained similar to that in 1, except that the oxime protons of the ligand were replaced with two methyl groups and a bridging -BPh2 moiety, respectively. X-ray structures of the FeII complexes (1a and 3a) revealed similar Fe-N distances; however, they were slightly elongated in 2a. The FeIII/FeII potential of 1, 2, and 3 appeared at -0.31 V, -0.25 V, and 0.07 V vs. Fc+/Fc, respectively, implying that HL and Me2L have comparable donor properties. However, BPh2L is more electron deficient than HL or Me2L. 1 showed electrocatalytic oxygen reduction reaction (ORR) activity in acetonitrile in the presence of trifluoroacetic acid (TFAH) as the proton source at Ecat/2 = -0.45 V and revealed selective 4e-/4H+ reduction of O2 to H2O. 1 showed an effective overpotential (ηeff) of 0.98 V and turnover frequency (TOFmax) of 1.02 × 103 s-1. Kinetic studies revealed a kcat of 2.7 × 107 M-2 s-1. Strikingly, 2 and 3 remained inactive for electrocatalytic ORR, which established the essential role of the oxime scaffolds in the electrocatalytic ORR of 1. Furthermore, a chemical ORR of 1 has been investigated using decamethylferrocene as the electron source. For 1, a similar rate equation was noted to that of the electrocatalytic pathway. A kcat of 6.07 × 104 M-2 s-1 was found chemically. Complex 2, however, underwent a very slow chemical ORR. Complex 3 chemically enhances the 4e-/4H+ reduction of O2 and exhibits a TOF of 0.24 s-1 and a kcat value of 2.47 × 102 M-1 s-1. Based on the experimental observations, we demonstrate that the oxime backbone of the ligand in 1 works as a proton exchanging site in the 4e-/4H+ reduction of O2. The study describes how the ORR is affected by the tuning of the ligand scaffold in a family of non-heme Fe complexes.

Construction of a BiVO4/VS-MoS2 S-scheme heterojunction for efficient photocatalytic nitrogen fixation.

Photocatalytic nitrogen (N2) reduction to ammonia (NH3), adopting H2O as the electron source, suffers from low efficiency owing to the sluggish kinetics of N2 reduction and the requirement of a substantial thermodynamic driving force. Herein, we present a straightforward approach for the construction of an S-scheme heterojunction of BiVO4/VS-MoS2 to successfully achieve photocatalytic N2 fixation, which is manufactured by coupling an N2-activation component (VS-MoS2 nanosheet) and water-oxidation module (BiVO4 nanocrystal) through electrostatic self-assembly. The VS-MoS2 nanosheet, enriched with sulfur vacancies, plays a pivotal role in facilitating N2 adsorption and activation. Additionally, the construction of the S-scheme heterojunction enhances the driving force for water oxidation and improves charge separation. Under simulated sunlight irradiation (100 mW cm-2), BiVO4/VS-MoS2 exhibits efficient photocatalytic N2 reduction activity with H2O as the proton source, yielding NH3 at a rate of 132.8 μmol g-1 h-1, nearly 7 times higher than that of pure VS-MoS2. This study serves as a noteworthy example of efficient N2 reduction to NH3 under mild conditions.

Mechanochemistry enabling highly efficient Birch reduction using sodium lumps and d-(+)-glucose.

In this study, a mechanochemical protocol for highly efficient and ammonia-free sodium-based Birch reduction was developed, leveraging the use of cheap and easy-to-handle sodium lumps. The key to achieving this transformation is the use of d-(+)-glucose as a proton source, which solidifies the reaction mixture in bulk state, enhancing the efficiency of the in situ mechanical activation of sodium lumps through the ball-milling process. Under the developed conditions, a diverse array of aromatic and heteroaromatic compounds were selectively reduced to produce the corresponding 1,4-cyclohexadiene derivatives in high yields within 30 min. Notably, all synthetic operations can be carried out without inert gases or the need for dry or bulk organic solvents. Furthermore, a scaled-up synthesis can be conducted without any yield losses. These results suggest that the present mechanochemical approach offers a more convenient, economically attractive, and sustainable alternative to previously established Birch reduction protocols.

Catalytic dinitrogen reduction to hydrazine and ammonia using Cr(N2)2(diphosphine)2 complexes.

The synthesis, characterization of trans-[Cr(N2)2(depe)2] (1) is described. 1 and trans-[Cr(N2)2(dmpe)2] (2) catalyze the reduction of N2 to N2H4 and NH3 in THF using SmI2 and H2O or ethylene glycol as proton sources. 2 produces the highest total fixed N for a molecular Cr catalyst to date.

Assessing plasmon-induced reactions by a combined quantum chemical-quantum/classical hybrid approach.

Plasmon-driven reactions on metal nanoparticles feature rich and complex mechanistic contributions, involving a manifold of electronic states, near-field enhancement, and heat, among others. Although localized surface plasmon resonances are believed to initiate these reactions, the complex reactivity demands deeper exploration. This computational study investigates factors influencing chemical processes on plasmonic nanoparticles, exemplified by protonation of 4-mercaptopyridine (4-MPY) on silver nanoparticles. We examine the impact of molecular binding modes and molecule-molecule interactions on the nanoparticle's surface, near-field electromagnetic effects, and charge-transfer phenomena. Two proton sources were considered at ambient conditions, molecular hydrogen and water. Our findings reveal that the substrate's binding mode significantly affects not only the energy barriers governing the thermodynamics and kinetics of the reaction but also determine the directionality of light-driven charge-transfer at the 4-MPY-Ag interface, pivotal in the chemical contribution involved in the reaction mechanism. In addition, significant field enhancement surrounding the adsorbed molecule is observed (eletromagnetic contribution) which was found insufficient to modify the ground state thermodynamics. Instead, it initiates and amplifies light-driven charge-transfer and thus modulates the excited states' reactivity in the plasmonic-molecular hybrid system. This research elucidates protonation mechanisms on silver surfaces, highlighting the role of molecular-surface and molecule-molecule-surface orientation in plasmon-catalysis.