Dissociation Of Molecules Research Articles

Global Optimization of Molybdenum Subnanoclusters on Graphene: A Consistent Approach toward Catalytic Applications.

The development of novel subnanometer clusters (SNCs) catalysts with superior catalytic performance depends on the precise control of clusters' atomistic sizes, shapes, and accurate deposition onto surfaces. The intrinsic complexity of the adsorption process complicates the ability to achieve an atomistic understanding of the most relevant structure-reactivity relationships hampering the rational design of novel catalytic materials. In most cases, existing computational approaches rely on just a few structures to draw conclusions on clusters' reactivity thereby neglecting the complexity of the existing energy landscapes thus leading to insufficient sampling and, most likely, unreliable predictions. Moreover, modeling of the actual experimental procedure that is responsible for the deposition of SNCs on surfaces is often not done even though in some cases this procedure may enhance the significance of certain (e.g., metastable) adsorption geometries. This study proposes a novel systematic approach that utilizes global search techniques, specifically, the particle swarm optimization (PSO) method, in conjunction with ab initio calculations, to simulate all stages in the beam experiments, from predicting the most relevant SNCs structures in the beam and on a surface, to their reactivity. To illustrate the main steps of our approach, we consider the deposition of Molybdenum SNC of 6 Mo atoms on a free-standing graphene surface, as well as their catalytic properties with respect to the CO molecule dissociation reaction. Even though our calculations are not exhaustive and serve only to produce an illustration of the method, they are still able to provide insight into the complicated energy landscape of Mo SNCs on graphene demonstrating the catalytic activity of Mo SNCs and the importance of performing statistical sampling of available configurations. This study establishes a reliable procedure for performing theoretical rational design predictions.

Observation of sequential three-body dissociation of camphor molecule—a native frame approach

Abstract The three-body dissociation dynamics of the dicationic camphor molecule (C10H16O2+) resulting from Auger decay are investigated using soft x-ray synchrotron radiation. A photoelectron-photoion-photoion coincidence method, a combination of a velocity map imaging spectrometer and a time-of-flight spectrometer is employed to measure the 3D momenta of ions detected in coincidence. The ion mass spectra and the ion–ion coincidence map at photon energies of 287.9 eV (below the C 1s ionization potential) and 292.4 eV (above the C 1s ionization potential for skeletal carbon) reveal that fragmentation depends on the final dicationic state rather than the initial excitation. Using the native frame method, three new fragmentation channels are discussed; (1) CH2CO+ + C7H 11 + + CH3, (2) CH 3 + + C7H 11 + + CH2CO, and (3) C2H 5 + + C6H 9 + + CH2CO. The dominating nature of sequential decay with deferred charge separation is clearly evidenced in all three channels. The results are discussed based on the experimental angular distributions and momenta distributions, corroborated by geometry optimization of the ground, monocationic, and dicationic camphor molecule.

High-Density Atomic Level Defect Engineering of 2D Fe-Based Metal-Organic Frameworks Boosts Oxygen and Hydrogen Evolution Reactions.

Electrocatalysts based on metal-organic frameworks (MOFs) attracted significant attention for water splitting, while the transition between MOFs and metal oxyhydroxide poses a great challenge in identifying authentic active sites and long-term stability. Herein, we employ on-purpose defect engineering to create high-density atomic level defects on two-dimensional Fe-MOFs. The coordination number of Fe changes from 6 to 4.46, and over 28% of unsaturated Fe sites are formed in the optimized Fe-MOF. In situ characterizations of the most optimized Fe-MOF0.3 electrocatalyst during the oxygen evolution reaction (OER) process using Fourier transform infrared and Raman spectroscopy have revealed that some Fe unsaturated sites become oxidized with a concomitant dissociation of water molecules, causing generation of the crucial *OH intermediates and Fe oxyhydroxide. Moreover, the presence of Fe oxyhydroxide is compatible with the Volmer and Heyrovsky steps during the hydrogen evolution reaction (HER) process, which lower its energy barrier and accelerate the kinetics. As a result, the optimized Fe-MOF electrodes delivered remarkable OER (259 mV at 10 mA cm-2) and HER (36 mV at 10 mA cm-2) performance. Our study offers comprehensive understanding of the effect of phase transformation on the electrocatalytic process of MOF-based materials.

VOCs conversion in He/H2O plasma produced in a micro-capillary tube at atmospheric pressure

Abstract A non-equilibrium plasma is created in a micro-capillary quartz tube (800 µm of internal diameter), by a DC-pulsed micro-dielectric barrier discharge (micro-DBD) and the propagation of an ionisation wave, in mixtures of He/H2O/VOC at atmospheric pressure where the studied volatile organic compounds (VOCs) are representative of molecules belonging to different chemical families: alcohols (methanol, ethanol, isopropanol, tert-butanol), ketones (acetone), nitriles (acetonitrile), and aromatic hydrocarbons (toluene). The conversion efficiency of these VOCs is studied as a function of the applied voltage on the micro-DBD (or electrical energy deposited in the plasma) and of the initial concentration of the molecules in the range from 1 ppm up to 3000 ppm (depending on the molecule), with the help of high-resolution real-time mass spectrometry Fourier transform ion cyclotron resonance associated to chemical ionisation (CI-FTICR) using H3O+ as precursor ion. A variety of by-products resulting from the conversion of VOCs are identified and quantified, emphasising that the micro-capillary plasma is able to induce a complex chemical reactivity. A qualitative analysis of the involved kinetics, based on the existing literature, reveals that helium species (ions and metastable states) and radicals coming from the dissociation of the water molecules (O and OH) are the most probable candidates to explain the formation of all compounds detected by the CI-FTICR apparatus. Quenching processes of the metastable He(23S) by the VOCs, leading to the dissociation of the molecules, are suggested to explain some of the experimental results.

Effective Screening of Metal Dopants for In2O3 Catalyst to Tune Catalytic Performance of CO2 Hydrogenation to Formic Acid

The metal doping is an effective strategy to adjust catalytic performance for indium oxide catalyst in CO2 hydrogenation. In current work, a series dopant, Co, Fe, Ni, Pd, Pt, Rh and Ru, are selected and examined in CO2 hydrogenation to formic acid by DFT based microkinetic simulation. It is found that substitutional doping is local effect which mainly promotes the reactivity of adjacent oxygen atoms. The calculations of both CO2 adsorption and hydrogen molecule dissociation certify the positive effects induced by doping, and the adsorption energy of CO2 has a linear relation with the transferred charges for all investigated catalysts which helps to explain the C‐O bond activation mechanism. Two pathways, Formate and Carboxyl, are investigated under same footing. It is noted that doping significantly reduces the hydrogenation barriers on two pathways compared with undoped surfaces. Moreover, the calculated TOF of formic acid formation is greatly increased on doped surfaces and Pt, Pd, Ru are identified as the most active dopants. In the end, it is concluded that reaction obeys Carboxyl mechanism and a valid descriptor of trans‐HCOOH* and H* formation energy is proposed for the screening of effective dopants.

The Performance of Ethylene Partial Oxidation on Group IB Metal Stepped Surfaces

Group IB metal catalysts, particularly Ag, Au, and Cu, exhibit particular selectivity for ethylene oxide (EO) formation, while Ag demonstrating the highest performance so far. Previous studies have explored the EO formation mechanism on (100) and (111) surfaces of group IB metals, but the reaction mechanism on the (211) facet (analogous to the edge sites of a catalyst particle) remains poorly understood. Herein, we fill in the knowledge gap by analyzing ethylene partial oxidation to EO on the (211) surfaces of Ag, Au, and Cu through density functional theory (DFT) calculations, scaling relationship analysis, and microkinetic modeling. Our study demonstrates that the (211) surface decreases the energy barrier for the dissociation of oxygen molecules into oxygen atoms, while unfavorable for the production of EO. Therefore, we should preserve an appropriate concentration of (211) surface on the nanoparticles when designing catalysts for the ethylene epoxidation reaction.

Boosting photocatalytic nitrogen fixation performance by adjusting the intramolecular D-A structure and band gap of thiophene-based COFs

Herein, we successfully synthesized two photoactive donor–acceptor (D-A) covalent organic frameworks by incorporating electric-deficient triazine and electric-rich benzotrithiophene moieties into the framework. The introduction of sulfur atom and triazine unit significantly change the intrinsic band gap of JLNU-COFs, this leads to an expanded range of light absorption, encompassing wavelengths from ultraviolet to visible. The narrow band gap of JLNU-311 allows for efficient utilization of visible light while maintaining the thermodynamic activity required for nitrogen reduction within appropriate energy bands. JLNU-311 modified with strong electron absorbing groups has higher activity to NH3 production without co-catalyst or sacrificial agent, and yield can reach 325.6 µmol/g/h. Theoretical calculation further confirm that acceptor structure can effectively regulate the band gap width, promote the adsorption, dissociation and protonation of N2 molecules on JLNU-COFs, and thus reduce the energy barrier of photocatalytic nitrogen reduction reaction (PNRR). Therefore, this study provides an effective strategy for design of active nitrogen fixing photocatalysts.

Reveal the source of protons in aqueous hydrogen proton battery

In this work, we have discovered and investigated the reaction mechanism of Aqueous Hydrogen Proton Battery (AHPB), which differ from conventional rocking-chair batteries. The hydrogen protons in the battery reaction is provided by the dissociation of H2O molecules in the electrolyte. Thus, the charging and discharging processes of the battery are also accompanied by changes in electrolyte concentration. To explore this, we have designed a AHPBs with a 2 M Zn(ClO4)2 electrolyte. The experimental results demonstrate excellent performance of the AHPBs, with a discharge specific capacity of up to 700.6 mAh g−1 and a charge-discharge power conversion efficiency of 83.638 %. Both experimental and simulation results confirm that H+ in the battery is primarily provided by H2O molecules solvating Zn2+. As the electrolyte concentration increases, ClO4− replaces some of the solvating H2O molecules of Zn2+, resulting in the remaining unsaturated solvating H2O molecules having a stronger propensity for deprotonation, thus facilitating the release of H+. This elucidates the specific source of H+ in AHPBs.

Research on the modification of magnesium hydride by two-dimensional layered Mo2Ti2C3 MXene

One of the most important technologies for the sustainable development of energy in the future is solid-state hydrogen storage. This study employed etching methods to fabricate two-dimensional layered catalyst Mo2Ti2C3 MXene, which was compared with unetched MAX phases Mo2Ti2AlC3 and Ti3C2, as well as Mo2C. Through mechanical ball milling, these materials were mixed with MgH2 to prepare composite materials, including MgH2 + Ti2C3, MgH2 + Mo2C, MgH2 + Mo2Ti2AlC3, and MgH2 + Mo2Ti2C3. According to the study, Mo2Ti2C3 demonstrates the synergistic catalytic actions of Ti and Mo in contrast to Ti2C3 and Mo2C. The composite material MgH2 + Mo2Ti2C3 lowers the initial dehydrogenation temperature of MgH2 to 180 °C, which is 165 °C lower than pure MgH2. After 30 min at 250 °C, the dehydrogenation amount is approximately 5.85 wt%. Hydrogen absorption begins at 40 °C and reaches approximately 5.75 wt% at 150 °C. Additionally, it maintains a reversible hydrogen storage capacity of up to 96 % even after 20th cycles at 300 °C. This is because Mo2Ti2C3 has one less layer of Al than Mo2Ti2AlC3, which results in a wider interlayer spacing, more active sites for MgH2, and facilitates hydrogen molecule dissociation and recombination.

Enhanced gas sensing performance of ZnO and Pt-doped ZnO nanostructured films by chemical spray pyrolysis

This study focuses on the preparation and characterization of zinc oxide (ZO) and platinum-doped zinc oxide (Pt-ZO) nanostructured thin films using the chemical spray pyrolysis technique. Structural and morphological properties of the films were investigated via X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). To understand the semiconducting nature and carrier dynamics, UV-Vis spectroscopy, electrical conductivity measurements, and a static gas sensing system were employed. The films exhibited crystallization in the hexagonal wurtzite structure with a preferred orientation along the (002) plane. FESEM images revealed the presence of small bright particles, particularly abundant in the 5 wt% Pt-doped ZO thin film, indicating the presence of platinum catalysts. Electrical conductivity measurements confirmed the semiconducting nature of the films. Optical parameters such as band gap and absorption index were obtained from UV-Vis spectroscopy. Gas sensing performance towards liquefied petroleum gas (LPG) showed that the 5 wt% Pt-doped ZO thin film exhibited a high response (69.9) to a 50 ppm concentration of LPG at 350 °C. The gas response and recovery times were observed to be 8 s and 12 s, respectively. These results are attributed to interactions between LPG molecules and adsorbed oxygen species on the sensor surface. Platinum atoms on the oxide surface facilitate the formation of oxygen vacancies and the dissociation of oxygen molecules at low temperatures, leading to increased adsorption and reaction with LPG molecules. This results in significant changes in the sensor's resistance, thereby amplifying the sensor response. The findings demonstrate the potential of Pt-doped ZO thin films for practical gas sensing applications.

Assessing Solid Catalysts with Ionic Liquid Layers (SCILL) from Molecular Dynamics Simulations: On the Role of Local Charge Polarization.

Recent developments in molecular mechanics modelling of metal catalyst surfaces with interfaces to complex ad-layers or bulk liquids enable the study of 10 nm scale systems by molecular dynamics simulations of up to microseconds. Therein, electronic polarization as otherwise benchmarked by quantum calculations is mimicked via atom-centered partial charges that are adjusted dynamically to account for changes in local environment. Apart from thermal fluctuations, this encompasses molecule association and dissociation processes as well as externally applied voltage. Here, we elaborate the concept of employing the charge equilibration method to the molecular dynamics simulation of solid catalysts, namely metal surfaces and substrate-supported metal nanoparticles. This showcases the association of reactants and their interplay with local charge polarization upon co-adsorption of ionic liquids or application of external voltage - thus paving the way to understanding complex interfaces in (electro-)catalysis from molecular dynamics simulation.

Tunneling Mechanisms of Quinones in Photosynthetic Reaction Center–Light Harvesting 1 Supercomplexes

In photosynthesis, light energy is absorbed and transferred to the reaction center, ultimately leading to the reduction of quinone molecules through the electron transfer chain. The oxidation and reduction of quinones generate an electrochemical potential difference used for adenosine triphosphate synthesis. The trafficking of quinone/quinol molecules between electron transport components has been a long‐standing question. Here, an atomic‐level investigation into the molecular mechanism of quinol dissociation in the photosynthetic reaction center–light‐harvesting complex 1 (RC–LH1) supercomplexes from Rhodopseudomonas palustris, using classical molecular dynamics (MD) simulations combined with self‐random acceleration MD‐MD simulations and umbrella sampling methods, is conducted. Results reveal a significant increase in the mobility of quinone molecules upon reduction within RC–LH1, which is accompanied by conformational modifications in the local protein environment. Quinol molecules have a tendency to escape from RC–LH1 in a tail‐first mode, exhibiting channel selectivity, with distinct preferred dissociation pathways in the closed and open LH1 rings. Furthermore, comparative analysis of free energy profiles indicates that alternations in the protein environment accelerate the dissociation of quinol molecules through the open LH1 ring. In particular, aromatic amino acids form π‐stacking interactions with the quinol headgroup, resembling the key components in a conveyor belt system. This study provides insights into the molecular mechanisms that govern quinone/quinol exchange in bacterial photosynthesis and lays the framework for tuning electron flow and energy conversion to improve metabolic performance.

Dissociation of HBr in Water Clusters Based on a Hybrid Density Functional Approach.

The dissociation of acidic molecules within a microscopic water environment is crucial for understanding intermolecular interactions such as hydrogen bonding. This study explores the optimal configurations of HBr(H2O)n=1-7 using hybrid density functional theory. According to the different mixed cluster structures, the corresponding HBr bond lengths, single-point energies, and introduced proton-transfer parameters are computed and analyzed. The findings indicate that a minimum of three water molecules is necessary for the dissociation of HBr. Subsequently, this conclusion is reinforced through the decomposition of energy components between the acid molecule and water clusters, calculation of hydrogen bonding energies, and analysis of vibrational infrared spectroscopy.

Water orientation on platinum surfaces controlled by step sites.

In this work, the adsorption structure of deuterated water on the stepped platinum surface is studied under an ultra-high vacuum by using heterodyne-detected sum-frequency generation spectroscopy. On a pristine Pt(553), D2O molecules adsorbed at the step sites act as hydrogen bond (H-bond) donors to the adjacent terrace sites. This ensures the net D-down orientation at the terrace sites away from the steps. In particular, the pre-adsorption of oxygen atoms at the step sites significantly alters the D-down configuration. The oxygen pre-adsorption leads to a spontaneous dissociation of the post-adsorbed water molecules at the step to form hydroxyl (OD) species. Since the hydroxyl at the step acts as a strong H-bond acceptor, D2O at the terrace no longer maintains the D-down configuration and adopts flat-lying configurations, significantly reducing the number of D-down molecules at the terrace. Density-functional theoretical calculations support these pictures. This work demonstrates the critical role of steps in controlling the net orientation of the interfacial water and provides an important reference for future considerations of the reactions at electrochemical interfaces.

Positively Charged Hollow Co Nanoshells by Kirkendall Effect Stabilized by Electron Sink for Alkaline Water Dissociation.

While cobalt (Co) exhibits a comparable energy barrier for H* adsorption/desorption to platinum in theory, it is generally not suitable for alkaline hydrogen evolution reaction (HER) because of unfavorable water dissociation. Here, the Kirkendall effect is adopted to fabricate positive-charged hollow metal Co (PHCo) nanoshells that are stabilized by MoO2 and chainmail carbon as the electron sink. Compared to the zero-valent Co, the PHCo accelerates the water dissociation and changes the rate-determining step from Volmer to Heyrovsky process. Alkaline HER occurs with a low overpotential of 59.0mV at 10mAcm-2. Operando Raman and first principles calculations reveal that the interfacial water to the PHCo sites and the accelerated proton transfer are conducive to the adsorption and dissociation of H2O molecules. Meanwhile, the upshifted d-band center of PHCo optimizes the adsorption/desorption of H*. This work provides a unique synthesis of hollow Co nanoshells via the Kirkendall effect and insights to water dissociation on catalyst surfaces with tailored charge states.

Role of H2O Adsorption in CO Oxidation over Cerium-Oxide Cluster Anions (CeO2)nO- (n = 1-4).

Water (H2O) is ubiquitous in the environment and inevitably participates in many surface reactions, including CO oxidation. Acquiring a fundamental understanding of the roles of H2O molecules in CO oxidation poses a challenging but pivotal task in real-life catalysis. Herein, benefiting from state-of-the-art mass-spectrometric experiments and quantum chemical calculations, we identified that the dissociation of a H2O molecule on each of the cerium oxide cluster anions (CeO2)nO- (n = 1-4) at room temperature can create a new atomic oxygen radical (O•-) that then oxidizes a CO molecule. The size-dependent reactivity of H2O-mediated CO oxidation on (CeO2)nO- clusters was rationalized by the orbital compositions (O2p) and energies of the lowest unoccupied molecular orbitals of active O•- radicals modified by H2O dissociation. Our findings not only provide new insights into H2O-mediated CO oxidation but also demonstrate the importance of H2O in modulating the reactivity of the O•- radicals.

Unveiling the electron-induced ionization cross sections and fragmentation mechanisms of 3,4-dihydro-2H-pyran.

The interactions of electrons with molecular systems under various conditions are essential to interdisciplinary research fields extending over the fundamental and applied sciences. In particular, investigating electron-induced ionization and dissociation of molecules may shed light on the radiation damage to living cells, the physicochemical processes in interstellar environments, and reaction mechanisms occurring in combustion or plasma. We have, therefore, studied electron-induced ionization and dissociation of the gas phase 3,4-dihydro-2H-pyran (DHP), a cyclic ether appearing to be a viable moiety for developing efficient clinical pharmacokinetics and revealing the mechanisms of biofuel combustion. The mass spectra in the m/z = 10-90 mass range were measured at several different energies of the ionizing electron beam using mass spectrometry. The mass spectra of DHP at the same energies were simulated using on-the-fly semi-classical molecular dynamics (MD) within the framework of the QCxMS formalism. The MD settings were suitably adjusted until a good agreement with the experimental mass spectra intensities was achieved, thus enabling a reliable assignment of cations and unraveling the plausible fragmentation channels. Based on the measurement of the absolute total ionization cross section of DHP (18.1 ± 0.9) × 10-16cm2 at 100eV energy, the absolute total and partial ionization cross sections of DHP were determined in the 5-140eV electron energy. Moreover, a machine learning algorithm that was trained with measured cross sections from 25 different molecules was used to predict the total ionization cross section for DHP. Comparison of the machine learning simulation with the measured data showed acceptable agreement, similar to that achieved in past predictions of the algorithm.

Novel Graphene-Based Reversible Physisorption Materials for High Hydrogen Uptake

Carbon-based nanomaterials (graphene, carbon nanotube, microporous carbon, graphitic carbon etc.) are excellent H2 storage materials due to high molecular H2 uptake at the micropores and large H2 adsorption at the graphene network via the formation of dipoles in H2 molecules through London dispersion forces. On the other hand, incorporation of transition metal nanoparticles within the nanocarbon network facilitates dissociation of H2 molecules into constituents H-atoms over the metal nanoparticles, followed by diffusion into the carbon nano-matrix via ‘spill-over’ effect for polarization/hybridization of metal-hydrogen to create high H2 binding energy for high hydrogen adsorption. Therefore, a nanocomposite of graphene-microporous carbon-metal nanoparticle network is expected to deliver excellent H2 uptake capacity and acts as a novel reversible physisorption material for hydrogen storage applications, which is very important for sustainable renewable energy integration.A simple, cost effective sputtering method is used to fabricate metal incorporated graphitic microporous carbon film and differential resistance measurement showed high H2 uptake. Average number of graphene layer formation is dependent on sputtering parameters, which manifest bi-to-multilayer graphene. With increase in graphene layers, H2 adsorption also increases due to a fourfold effect: higher molecular hydrogen uptake at the graphene layers, more active sites into the micropores, promotion of molecular dissociation into atomic hydrogen by the metal nanoparticles, and the formation of hydrogenated carbon via destruction of the π-bonds.

(Invited) Development of Multifunctional Nanoscale Reactors for Electrocatalytic Oxidation of Dimethyl Ether Fuel

There has been growing interest in utilizing small (simple) organic molecules, as alternative fuels to hydrogen, for electrochemical energy conversion in fuel cells. Dimethyl ether (DME) is one of the possible choices in this respect. But electrooxidation of DME is rather slow at ambient conditions. Obviously, there is a need to develop novel electrocatalytic materials.Bimetallic PtSn catalysts were found to be almost as active as PtRu for methanol oxidation, and PtSn was even more efficient toward the electrooxidation of ethanol where breaking of C-C bond is required. While PtRu forms a single-phase homogeneous (intermetallic) alloy in which Ru is largely metallic, tin does not maintain its metallic state in PtSn (heterogenous alloy) and is transformed readily to such oxygenated species as Sn oxides or hydroxides. During operation of PtSn, the Pt component retains its mostly metallic character and act independently as Pt0 catalyst. By analogy to Ru, the Sn “bifunctional agent” tends to activate the water dissociative adsorption and increases population of chemisorbed hydroxyl groups to diminish the Pt-poisoning effect through enhanced oxidation of CO-type intermediates. Nevertheless, the DME oxidation on both PtRu or PtSn is still kinetically less favorable, relative to the systems’ performance toward methanol. While Sn, and particularly Ru alloyed atoms activate readily the water dissociative adsorption on Pt and permit the oxidative stripping of the poisoning CO-type adsorbates, the feasibility of the enhancement of the of the DME adsorption and activation through alteration of the electronic structure of Pt catalytic sites has not been fully explained. By analogy to the ethanol oxidation, Pt sites in the heterogeneous PtSn alloy are active toward dissociation of the DME molecule but the Sn additive is less efficient than Ru (from intermetallic PtRu) in the oxidative removal of poisoning adsorbates. But PtRu is probably the most active during oxidation of methanol, and this small organic molecule is also the DME-oxidation-reaction intermediate. Nevertheless, in comparison to bare Pt, electrooxidation of DME starts at PtRu and PtSn at less positive potentials.We pursue a concept of utilization of multicomponent hybrid electrocatalytic systems or nanoreactors utilizing zirconia oxide matrices for supporting and activation of primarily PtSn nanoparticles supported onto Vulcan XC-72 carbon black carriers. Electrocatalytic activity of Vulcan-supported PtSn (PtSn/V) nanostructured alloys supported onto ZrO2 matrices has been significantly enhanced toward electrooxidation of DME in acid medium (0.5 mol dm-3 H2SO4) by decorating PtSn/V with bimetallic PtRu nanoparticles. The enhancement effect concerns both shifting the onset potential for the DME-oxidation toward less positive values and increase of the DME electrocatalytic current densities recorded under both cyclic voltammetric and chronoamperometric conditions. The activating capabilities of ruthenium nanostructures seem to originate from the existence (even below 0.45 V vs. RHE) of reactive ruthenium oxo/ hydroxo groups on their surfaces capable of inducing the oxidative removal of poisoning (CO-type) adsorbates from the neighboring platinum catalytic sites. In this respect, the Ru-oxo species seem to support activity of Sn forming with Pt the PtSn heterogenous alloy. The PtSn/V admixed with PtRu decorated ZrO2 exhibit very high activity toward the oxidation of methanol which is also an important DME-oxidation intermediate. On the whole, the hybrid materials composed of Vulcan-supported PtSn decorated with Ru or PtRu nanoparticles decorated zirconia oxide seem to act as multifunctional nanoreactors inducing not only stripping of poisoning adsorbates but also catalyzing oxidation of the DME-reaction intermediates (methanol). Acknowledgement Authors acknowledge financial support of the National Science Center (Poland) under Opus Project 2018/29/B/ST5/02627.

Enhanced photocatalytic CO2 conversion into reusable fuels with efficient solid-state proton donors

Lead halide perovskites driven photocatalytic CO2 reduction reaction (CO2RR) is restricted by H2O proton source due to the poor water-resistance of perovskites and difficult dissociation of H2O molecules. In this paper, a novel solid-state proton donor of amino acid modified melamine foam (Ami-MF) is developed, which could improve CO2RR of CsPbBr3/Bi2WO6 S-scheme heterojunction. On the one hand, amino acid molecules possess abundant –COOH and –NH2 groups, which are broken easily by catalyst oxidation compared with H2O, supplying sufficient protons for CO2RR. Product yield of Glu-MF/CsPbBr3/Bi2WO6 reaches 112.81 μmol/g/h, which is 3.8 times higher than that (29.83 μmol/g/h) of H2O-MF/CsPbBr3/Bi2WO6. Moreover, glutamic acid (Glu), cysteine (Cys), arginine (Arg) as typical acidic, neutral and basic amino acids are selected to explore proton supply from different amino acids. Glu-MF/CsPbBr3/Bi2WO6 exhibits the best CO2RR than other two Ami-MF, ascribing to the dicarboxylic structure of Glu. On the other hand, MF is an integral part in solid-state proton donor. Product yield of Glu-MF/CsPbBr3/Bi2WO6 is about 46.2 times higher than that (2.44 μmol/g/h) of powdery Glu/CsPbBr3/Bi2WO6, which ascribes to the efficient gas–solid CO2RR system induced by the three-dimensionality and porosity of MF. This study develops an efficient solid proton donor to enhance perovskites driven CO2RR.