Catalyst For Reduction Research Articles

Influence of Carbon Nanotube Support on Electrochemical Nitrate Reduction Catalyzed by a Cobalt Complex

Access to clean water is a pressing environmental and public health concern. Excess nitrate (NO3 -) from the overuse of fertilizer finds its way into our surface water and groundwater, which leads to adverse health effects such as cancer and causes significant damage to ecosystems.1-4 The electrochemical nitrate reduction reaction (NO3RR) has emerged as a promising water treatment approach to address this issue. The NO3RR involves the transformation of waste NO3 - into value-added nitrogen species, such as ammonia (NH3), via reduction. NH3 serves as a valuable chemical in various applications, including its use as a fertilizer, chemical precursor, fuel, and a potential hydrogen (H2) carrier for energy storage and transportation.5-7 Leveraging renewable energy, the NO3RR provides a sustainable approach to distributed NH3 production, which stands in stark contrast to the energy-intensive Haber-Bosch process.8-10 As a result, there is growing interest in designing catalysts for the selective reduction of NO3 - to NH3. However, this requires that we obtain a clear understanding of the role of each component in the catalyst structure.Molecular catalysts have unique advantages over other electrocatalytic materials due to their well-defined structures, which can be tailored through the choice of the metal center and ligands.11,12 Moreover, molecular catalysts can be immobilized on substrates to create heterogeneous electrocatalysts capable of achieving a high current density.13,14 In previous investigations, we showcased the efficacy of multi-walled carbon nanotubes (CNTs) as a catalyst support for electrochemical carbon dioxide reduction reactions.13,15 In heterogenized molecular catalysts, CNTs are generally believed to provide high surface area and electron conduction. However, our recent investigation reveals that CNTs can serve as catalysts themselves for the NO3RR,16 which expands our understanding of the diverse roles CNTs play in NO3 - reduction electrocatalysis.A major challenge in the field of electrocatalysis is the development of catalyst design strategies to control the reaction selectivity. We report on an underexplored approach to overcome this challenge by tuning the CNT support for a cobalt complex. With pristine CNTs as the support, the cobalt complex/CNT hybrid catalyst is selective for NO3 - reduction to NH3 with a maximum Faradaic efficiency of 70%. In contrast, the cobalt complex supported on oxidized CNTs (OCNTs) generates mostly H2 under the same conditions. On the basis of kinetic measurements which reveal that the rate-determining step of NO3 – reduction is limited by the first electron transfer without involving a proton, we propose that the oxygen functional groups on the OCNT support help deliver protons and steer the supported cobalt complexes from catalyzing NO3 - reduction to H2 evolution. The performance of both of these hybrid catalysts is compared with the controls of bare CNTs and OCNTs. Additional control experiments include tests conducted in the absence of NO3 -. These control experiments together with the rest of the experimental data provide strong evidence to support the notion that the product selectivity of the NO3RR catalyzed by cobalt complexes can be controlled via the CNT support. This study demonstrates the importance of tailoring the catalyst support to advance reactivity in catalysis for environmental remediation.

(Invited) Fundamentals of Single Atom Alloy Catalysts for Electrochemical Nitrate Reduction to Ammonia

Electrochemical conversion of toxic nitrate into useful ammonia provides a route to remediating the most frequent water pollutant while simultaneously generating one of the most produced bulk chemicals. While highly desirable, this conversion is plagued by complications including a highly branching reaction pathway - which can produce highly toxic undesirable products, the need to reduce a negatively charged species, a relatively low nitrate concentration, and competition for electrons between nitrate reduction and parasitic hydrogen evolution. Therefore, electrocatalysts must be developed which are highly selective not only for nitrate over other species in the water matrix, but also selective to the desired ammonia product. Single atom alloy catalysts, where a single atom of one element is embedded in a solvating phase of a secondary element, provides an opportunity to engineer catalysts with atomic level precision. In this presentation, we will outline the fundamental behavior of single atom alloy for nitrate reduction. We explore this topic through density functional theory calculations of the reaction mechanisms, including thermodynamics and kinetic aspects. Particularly, we will discuss the effect of single atom identity, effect of matrix element, and pH and potential. We show that the ability of the single atom to localize the N* species drives the reduction towards ammonia formation, as exemplified by Ru in Cu, while facile exchange of N* between the single atom site and the matrix leads to the formation of N2 or other undesirable products, as exemplified by Pd in Cu and Au in Cu, respectively. We also discuss the importance of the selection of the solvating element; for example, Cu is a good solvating metal because it is a good conductor, while minimizing the hydrogen evolution reaction. Further, we discuss the limits of pH and potential on the performance. In general, higher pH and more moderately negative potentials favor nitrate reduction to NH3 or N2, while lower pH and more negative potentials drive H2 evolution, and generation of NOx species.

A Durable Vanadium Disulfide-Based Catalyst for Nitrate Reduction and Insights on in-Line Ammonia Detection By Mass Spectrometry

Ammonia is critical to agriculture worldwide and is a renewable fuel. The dominant process for ammonia synthesis, Haber-Bosch, is fossil-fuel dependent, energy intensive and highly centralized. Electrochemical N2 or NO3 - reduction promises to provide a decentralized and environmentally friendly route to ammonia synthesis. Electrochemical ammonia synthesis research is challenging due to typically low amounts of ammonia produced relative to environmental levels. In this two-part presentation, a VS2-based nitrate reduction catalyst, which has shown exceptional activity, selectivity, and durability, will be discussed. The proposed mechanism of nitrate reduction on VS2 will be discussed along with thorough characterization of the catalyst material, and we will present density functional theory mechanistic insight of nitrate reduction on VS2. Various experimental controls used in the VS2 nitrate reduction experiments, including Ar purge and NMR characterization experiments will also be detailed. Additionally, a test platform for nitrogen or nitrate reduction catalysts in a gas-diffusion electrode architecture with in-line NH3 and 15NH3 monitoring by multi-turn TOF-MS will be discussed. This part of the presentation will detail some advantages of our analytical approach that stem from the low limit of detection and high mass resolution. Finally, we will address areas of opportunity in electrochemical ammonia generation.

Probing the Depths of Electrocatalysis Systems: X-Ray Absorption Spectroscopy Reveals Catalyst Behavior

X-ray absorption spectroscopy (XAS) is a powerful experimental technique used to study the electronic structure and local environment of atoms in a material. It provides valuable insights into the chemical bonding, oxidation states, and coordination geometry of elements. XAS has been widely applied in various fields of electrochemistry, including popular topics like the hydrogen evolution reaction (HER), oxygen reduction reaction (ORR), and CO2 reduction reaction (CO2RR).Despite the growing recognition of the practical importance of XAS techniques, correlating experimental spectroscopy with the working mechanisms and deciphering the structure of the electrochemical interface under reaction conditions remains challenging. In the case of CO2RR, we utilized operando XAS to investigate multiple Cu-based catalysts in different cell configurations. Our findings revealed that altering the reaction environment can induce an alternative pathway for catalyst structural changes. Moreover, operando XAS demonstrated that the reduction of Cu oxide catalysts is not solely governed by applied potentials but is also influenced by mass transport and other parameters. For ORR, in situ XAS not only provides information about the local environment changes of Pt-based catalysts but also unveils surface properties through △μ-X-ray adsorption near-edge spectroscopy (△μ-XANES). This further aids in the discovery of degradation mechanisms in proton exchange membrane fuel cells (PEMFCs). In the case of HER, in situ XAS enables characterization beyond catalysts and extends to the electrochemical interface.Overall, XAS techniques play a crucial role in understanding the electronic structure and local environment of atoms in electrochemical systems, shedding light on reaction mechanisms and catalyst performance under realistic conditions Acknowledgement The authors thank the funding source from Liquid Sunlight Alliance under the U.S. DOE, Office of Science, Office of Basic Energy Sciences, Fuels Award Number DE-SC0021266 and the Laboratory Directed Research and Development Program of the Lawrence Berkeley National Laboratory under the U.S. DOE Contract No. DE-AC02-05CH11231.

Size and Electronic Effects on Redox Potentials and Electrocatalytic Processes Performed by Corrole-Chelated Metal Complexes

The future of our planet critically depends on the introduction of new or improved strategies for developing non-polluting energy production. Leading approaches are the electrocatalytic production of hydrogen gas, development of fuel cells relying on efficient reduction of oxygen and either gaseous or liquid fuels, as well as efficient reduction of carbon dioxide. Metal complexes chelated by N4 macrocycles serve as excellent catalysts in many of these processes, performed at both homogeneous and heterogeneous conditions. Our contributions to those aspect focused on introducing metallocorroles as catalysts for reduction of protons, oxygen and carbon dioxide, as well as for water oxidation [1-5]. The common motif in these and other publications was to take advantage of the relatively easy functionalization of the macrocyclic periphery for the tuning of properties and reactivity. A significant game changer was the recently reported synthetic access to corroles with meso-CF3 substituents and even to the parent corrole with no substituents whatsoever [6]. These developments allow for a focus on the size effect, which according to both hypothesis and fast accumulating results has a very strong effect (“smaller is better”) on the performance of electrodes modified by the corresponding metal complexes [7-9].References Sinha, N. Fridman, Y. Diskin-Posner, L. J. W. Shimon and Z. Gross “Superstructured Metallocorroles for Electrochemical CO2 Reduction”, Chem. Commun. 2019, 55, 11912-11915.Sinha, A. Mahammed, N. Fridman and Z. Gross “Water Oxidation Catalysis by Mono- and Binuclear Iron Corroles” ACS Catal. 2020, 10,3764-3772.Sudhakar, A. Mahammed, Q.-C. Chen, N. Fridman, B. Tumanskii and Z. Gross “Copper Complexes of CF3‐Substituted Corroles for Affecting Redox Potentials and Electrocatalysis” ACS Appl. Energy Mater. 2020, 3, 2828-2836.Yadav, I. Nigel-Etinger, A. Kumar, A. Mizrahi, A. Mahammed, N. Fridman, S. Lipstman,I. Goldberg, and Z. Gross “Hydrogen Evolution Catalysis, by Terminal Molybdenum-Oxo Complexes”, Iscience 2021, 24, 102924.-C. Chen, S. Fite, N. Fridman, B. Tumanskii, A. Mahammed, and Z. Gross “Hydrogen Evolution Catalyzed by Corrole-Chelated Nickel Complexes, Characterized in all Catalysis-relevant Oxidation States”, ACS Catalysis 2022, 12, 4310−4317.Kumar, P. Yadav, M. Majdoub, I. Saltsman, N. Fridman, S. Kumar, A. Kumar,A. Mahammed and Z. Gross “Corroles: The Hitherto Elusive Parent Macrocycle and its Metal Complexes” Angew. Chem. 2021, 60, 25097-25103. Mahammed and Z. Gross “Milestones and Most Recent Advances in Corrole’s Science and Technology”, J. Am. Chem. Soc. 2023, 145, 12429–12445Raslin, J. Douglin, A. Kumar, M. Fernandez-Dela-Mora, D. Dekel and Z. Gross “Size and electronic effects on the performance of (corrolato)cobalt-modified electrodes for ORR catalysis”. Inorg. Chem. 2023, 62, 14147–14151.Kumar, S. Fite, A. Raslin, S. Kumar, A. Mizrahi, A. Mahammed, and Z. Gross “Beneficial Effects on the Cobalt-Catalyzed Hydrogen Evolution Reaction Induced by Corrole Chelation”. ACS Catal. 2023, 13, 13344-13353. Figure 1

Homogenized Modeling of CO2/CO Reduction Catalyst Microenvironments with Intermixed Hydrophobic and Hydrophilic Regions

Electroreduction of CO and CO2 offer a pathway toward renewable-powered synthesis of hydrocarbon chemicals and fuels. Both the composition and the structure of cathodic catalyst microenvironments in gas diffusion electrodes play a dominant role in determining the product composition and efficiency metrics. Porous and hydrophilic copper environments are known to produce multi-carbon species and exhibit large active surface areas, but recent investigations have shown that the inclusion of sporadically-distributed porous hydrophobic regions creates additional pathways for the delivery of gaseous reactants, thereby mitigating transport limitations seen in pure Cu catalysts.As the design space for catalysts has grown to include a wide variety of material and geometric parameters, accurate PDE-based modeling and simulation of such systems has become necessary to understand and optimize the coupled reaction and transport processes that determine cell performance. High fidelity models, however, pose immense computational challenges. Physical and chemical processes occur over a wide variety of spatiotemporal scales, ranging from pore-scale reaction and transport to device-scale gradients in species concentrations. Additionally, the spatial orientation of these features necessitates modeling in multiple dimensions, and transport occurs simultaneously through two phases located within randomly-intermixed porous regions. As a result of all these factors, numerical simulation of high fidelity models is prohibitively expensive.In this work, we develop, numerically simulate, and validate a predictive model that efficiently incorporates a wide range of physical and chemical processes occurring in catalyst microenvironments with intermixed hydrophobic and hydrophilic regions. We employ homogenization as a means of model reduction, constructing a medium fidelity model that captures both microenvironment geometric scales and full device scales in 3D. Our model, coupled with the appropriate numerical methods for treatment of stiff and multi-dimensional problems, permits low-cost exploration of the high-dimensional parameter space associated with recently developed catalysts, offering quantitative insight into the optimal design of microenvironments for CO and CO2 electroreduction.This work is supported by the United States Department of Energy under grant DE-SC0021633.

Challenges and Opportunities in Preparing Fe-N-C Layers Supported on Non-Carbon Supports

Global energy demand will be continuously rising in the foreseeable future. To mitigate the results of climate change it is necessary to reduce the emittance of greenhouse gases. One promising approach is to switch to hydrogen as energy carrier and use proton exchange membrane fuel cells (PEMFCs) to efficiently convert H2 into electric power. Here, hydrogen and oxygen/air are used to directly generate electrical energy with only water as byproduct. Both reactions need to happen efficiently at the same time. The oxygen reduction reaction (ORR), however, is a very sluggish four-electron-reaction and needs efficient catalysts.The state-of-the-art ORR catalyst in PEMFC is platinum but that is a very scarce and expensive metal. Hence, it is important to switch to precious-metal-group (PGM) free catalysts. In recent years, bio inspired iron-based FeNC catalysts have been shown to approach ORR activities that are competitive with those of platinum, even though they need a higher catalyst loading than Pt to reach the desired high current densities.1–3 Those catalysts feature single Fe atoms surrounded by four N atoms in graphitic carbon. The drawback of those materials is their lower stability compared to PGM materials. In a nutshell, the carbon matrix oxidizes during operation in PEMFCs, changing the morphology of the catalytic center and rendering it less active, or inactive, depending on the carbon oxidation extent. Direct demetallation phenomena are also possible, leaving a N4 cavity without metal cation center. It was shown recently by Wu et al.4 that it is possible to raise durability by adding an additional carbon layer on the catalyst. One alternative approach to reduce those degradations is to interface Fe-N4 sites with a carbon-free support. The targeted support material must be immune to corrosion in acid and withstand the typical ORR electrochemical potentials. It also has to be electrically conductive to facilitate electron transfers, both locally and on long scale.In this work, conductive ceramic metal oxide materials (Ta doped SnO2, TTO) was investigated as a possible alternative catalyst supports. This material is resistant to acid and can withstand prolonged potentials at operating conditions in PEMFCs.5 During the synthesis of the FeNC catalysts, high temperatures are generally applied. Such treatments can be detrimental to the conductivity of ceramics due to metal aggregation (in case of doped materials) and may also lead to morphological changes as well as the reduction of the ceramics to metallic materials. A robust method to synthesize FeNC catalysts is by mixing the separate Fe, N and C precursors and using optimized thermal treatment. In this study, the effect of the pyrolysis conditions as well as the ratio of FeNC precursors to TTO was investigated with various characterization methods, e.g. X-ray absorption spectroscopy, Mossbauer spectroscopy, and high resolution TEM. The characterization techniques confirm the presence of single atom Fe as well as different Sn species that might contribute to the activity. The resulting materials were electrochemically characterized with rotating disc electrode techniques and in PEM fuel cells for their ORR-activity and durability. It was shown that the activity of materials with a high FeNC precursor content relative to TTO can outperform a reference FeNC synthesized similarly but without TTO, in both RDE (Figure) and PEMFC.The presentation will report in detail the effects of pyrolysis conditions and FeNC precursor/TTO content on the structure, activity and stability of materials.(1) Mehmood, A. et al. High Loading of Single Atomic Iron Sites in Fe–NC Oxygen Reduction Catalysts for Proton Exchange Membrane Fuel Cells. Nat. Catal. 2022, 5 (4), 311–323. https://doi.org/10.1038/s41929-022-00772-9.(2) Gasteiger, H. A.; Marković, N. M. Just a Dream—or Future Reality? Science 2009, 324 (5923), 48–49. https://doi.org/10.1126/science.1172083.(3) Zion, N. et al.. Electrocatalysis of Oxygen Reduction Reaction in a Polymer Electrolyte Fuel Cell with a Covalent Framework of Iron Phthalocyanine Aerogel. ACS Appl. Energy Mater. 2022, 5 (7), 7997–8003. https://doi.org/10.1021/acsaem.2c00375.(4) Liu, S.et al. Atomically Dispersed Iron Sites with a Nitrogen–Carbon Coating as Highly Active and Durable Oxygen Reduction Catalysts for Fuel Cells. Nat. Energy 2022, 7 (7), 652–663. https://doi.org/10.1038/s41560-022-01062-1.(5) Jiménez-Morales, et al. Strong Interaction between Platinum Nanoparticles and Tantalum-Doped Tin Oxide Nanofibers and Its Activation and Stabilization Effects for Oxygen Reduction Reaction. ACS Catal. 2020, 10 (18), 10399–10411. https://doi.org/10.1021/acscatal.0c02220. Figure 1

Development of a Controlled Humidity Differential Electrochemical Gas Monitoring System

Lithium-air batteries (LABs) represent a promising future battery technology due to their high energy density, although several challenges hinder them from achieving their theoretical performance. These challenges include clogging of the porous air cathode by insoluble discharge products and high overpotentials during cycling [1, 2]. A recent proposal to address these issues involves the reversible formation and oxidation of LiOH in nonaqueous LABs. Of course, LiOH-based LABs require a proton source to form LiOH from the electrochemical reaction of oxygen and lithium ions [3]; humidity in air is an obvious choice for the proton source, making the relative humidity of LAB feed gas an important parameter to control and monitor during LAB electrochemical analysis.For LABs, galvanostatic charge/discharge coupled with quantitative gas evolution/consumption measurement is essential to understand the electrochemical processes during battery operation. Here, we report an advanced operando pressure measurement system that allows the control and monitoring of humidity in the cell headspace while also tracing overall gas consumption and evolution. Our gas handling system generates humid air using a water-containing chamber with a temperature control vessel to generate water vapor. A mass flow controller mixes dry air with humid air to generate specific relative humidity and send it to the cell. Using various low-volume in-line sensors, our system can track headspace humidity, temperature, and pressure within a custom-modified Swagelok-type cell. The total headspace volume must be small (~mL) since gas consumption occurs on a μmol scale in our lab-scale cells. To minimize headspace and dead volume within the Swagelok-type cell, a digital humidity and temperature sensor with exceptional accuracy was integrated into a customized printed circuit board (PCB). This PCB is attached to the small dead-volume Tee connection. To control the humidity inside the cell and achieve sensor data simultaneously, all sensors in the monitoring system are controlled by a LabVIEW program (National Instruments). To show the utility of this new system, we will present analyses of nonaqueous and solid-state LAB cells that operate at various humidities and current rates, while employing various known 2 e- and 4 e- oxygen reduction catalysts.

Electrochemical CO2 Reduction in the Presence of Flue Gas Impurities: Effect of NOx, SOx and O2

Electrochemically converting CO2 to valuable chemical products using renewable energy sources may present solutions to alter current increasing CO2 emission trends. Currently, electrolyzer research is almost exclusively done with pure CO2 streams that - in practice - would originate from carbon capture units that prevent CO2 release to the atmosphere [1]. The capture and purification steps are cost intensive processes which is why direct usage of flue gases that contain impurities is a highly interesting approach. For this reason, the performance of CO2 electrolyzers equipped with state-of-the-art Bi2O3 or Ag catalysts is investigated in this work with an impure CO2 feed stream containing SO2, NO or O2. The short-term effect of highly concentrated SO2 (10 000 ppm) and NO (8 300 ppm) impurities during CO2 electrolysis was previously described [2,3]. Our work [4] elaborates further on this matter through 20 h experiments with flue gas-like concentrations of 200 ppm SO2 or NO. The results show a stable operation without severe FE losses (remains >90%) and structural adaptations to neither Ag nor Bi2O3 by these impurities. The presence of oxygen in flue gas streams at concentrations of several percent is common and causes a major decrease in FE to the target products (CO or HCOO-) during electrolysis. This is a result of the competition between the ORR and CO2RR with the former occurring more preferentially. To overcome this, we have discovered two possible strategies, which allow high FE’s to CO2RR products even in the presence of oxygen. (1) By operating the electrolyzer at a sufficiently high overall current density, all of the O2 entering and reaching the electrode surface gets reduced, allowing the CO2RR to become the dominant reaction. Although this approach has a higher electricity penalty, the extra cost is negligible compared to the cost otherwise associated with the CO2 purification for CO2 streams with an O2 content below 3%. (2) Given that the ORR is mostly occurring at the carbon-based gas diffusion layers another approach to improve CO2RR efficiency in the presence of oxygen is to replace this conventional support with ultra hydrophobic PTFE membrane filters. Since they are inefficient oxygen reduction catalysts, CO2RR again takes up the major fraction of the applied current density. A downside of using PTFE is that an additional conductive layer is required in case the catalyst itself (e.g. for bismuth oxide) is not conductive enough. These results thus not only offer new insights into the impact of gaseous impurities during CO2 electrolysis, but also suggest a strategy to improve electrolyzer performance with O2-containing feed streams. Bibliography [1] Lee M.Y., Environ. Sci. and Technol.; DOI: 10.1080/10643389.2019.1631991[2] Luc W.; JACS, DOI: 10.1021/jacs.9b03215[3] Ko B., Nature Comm. DOI : 10.1038/s41467-020-19731-8[4] Van Daele S ., J. Appl. Catal. B, Environ.; DOI: 10.1016/J.APCATB.2023.123345 Figure 1

Developing Online ICP-MS Methodology for Examining Catalyst Degradation Dynamics during Electrochemical CO2 Reduction

The electrochemical CO2 reduction reaction (CO2RR) provides a path towards sustainable production of carbon-based fuels and chemicals, using renewable electricity to drive the conversion of CO2 into products such as ethylene, ethanol, and methane. A challenge limiting the implementation of CO2RR is catalyst stability during operation, and greater fundamental understanding is needed to uncover the governing physical, chemical, and electrochemical factors, as well as degradation mechanisms, operative under reducing conditions. One tool that can be used for conducting such fundamental studies is online inductively coupled plasma mass spectrometry (ICP-MS). In this study, an experimental framework was developed for using online ICP-MS for time-resolved degradation studies during CO2RR conditions. Using a customized flow cell setup, we coupled an ICP-MS to a potentiostat to simultaneously apply a potential or current while evaluating dynamics and degradation for both Au and Cu catalysts. Both ionic dissolution and degradation in the form of nanoparticle detachment can be detected and analyzed. The presence of nanoparticles is indicated by spikes in ICP-MS data. The intensity of the spikes is directly related to particle size. We used ICP-MS to determine particle mass, size distribution, and cumulative mass loss over time. We found the use of ICP-MS to obtain particle size distribution gave comparable results to transmission electron microscopy (TEM) determination of particle size distribution.Au foil as the CO2 reduction catalyst was used as a model system for detecting and quantifying degradation in situ using ICP-MS. We found Au degradation to occur in the form of nanoparticle detachment, with increasingly negative applied potential (0 V vs RHE to -1 V vs. RHE) in the presence of CO2 leading to increased number of nanoparticles in the electrolyte; however, no ionic dissolution was observed. In comparison, when the electrolyte was saturated with N2, nanoparticles detached from the electrode at a lower rate than in CO2-saturated conditions. We also examined Cu degradation under the same conditions as the Au system. Cu degradation occurs as both ionic dissolution and nanoparticle detachment, but under all conditions, Cu has less nanoparticle detachment and cumulative mass loss due to nanoparticles than Au. The developed experimental framework in this study would be translatable to a variety of electrocatalytic reactions and environments. Examination of catalyst degradation behavior in situ, including non-traditional degradation mechanisms such as nanoparticle detachment from bulk materials, can be used to obtain greater fundamental understanding of degradation mechanisms and rational design of materials with improved stability.

Direct Comparisons of Oxygen Electro-Reduction across Molecular and Extended Oxides

Our work is focused on understanding hydrogen transfer in redox-active metal oxides as candidates for next-generation catalytic architectures, using oxygen electro-reduction as a model reaction. We are specifically studying the interrelationships between hydrogen transfer electrocatalysis across what we term the “molecules-to-materials design continuum” by directly comparing electrochemical properties of molecular tungsten-based polyoxometalates (polyoxotungstates) and extended tungsten oxides.The goal of this study was to critically compare trends of activity and selectivity towards the two-electron oxygen reduction reaction using a series of three catalyst composites derived from molecular polyoxotungstates: (1) the intact molecule adsorbed on a conductive carbon support; (2) the same composite after thermal decomposition of the molecule to bulk WO3; and (3) an intermediate state comprising the partially decomposed molecule.Catalyst composites were synthesized by wet impregnation of the polyoxotungstate (TBA)4W10O32 (TBA = tetrabutylammonium) from acetonitrile on Vulcan carbon, targeting catalyst loadings that yield well-dispersed molecular units. We then used thermal treatments over a range of temperatures associated with progressive thermal decomposition to the intermediate and fully decomposed states. Thermal decomposition reactions and products were further characterized using thermogravimetric analysis and in-situ powder X-ray diffraction. Electrocatalytic measurements were made using standard analytical protocols comprising rotating-disk electrode voltammetry of carbon-supported catalysts deposited as thin films on glassy carbon substrates.On thermal treatment, we observed that the polyoxotungstate loses stabilizing counterions with progressive rearrangement into disordered clusters and ultimately crystalline nanoparticles of orthorhombic WO3. Each of these various forms exhibit broadly similar reactivity towards the oxygen reduction reaction. Electroanalytical results suggest all three tungsten-based composites are poor oxygen reduction catalysts with activities comparable to that of the carbon support. Nonetheless, Levich analysis suggests high selectivity for 2-electron conversion to H2O2 and catalytic onsets that correlate well with distinct voltametric features corresponding to H-activation and, in the case of extended oxides, bulk proton insertion. Ongoing work is focused on extending these studies toward more tractable hydrogen transfer reactions and identifying alternative catalysts with more thermodynamically accessible mechanisms for H activation.More broadly, we hypothesize that these types of apples-to-apples comparisons between molecular and extended catalysts will reveal vital information about the impact of active site composition and electronic structure on H-transfer catalysis.

Oxidative and Reductive Manipulation of C1 Resources by Bio-Inspired Molecular Catalysts to Produce Value-Added Chemicals.

ConspectusTo tackle the energy and environmental concerns the world faces, much attention is given to catalytic reactions converting methane (CH4) and carbon dioxide (CO2) as abundant C1 resources into value-added chemicals with high efficiency and selectivity. In the oxidative conversion of CH4 to methanol, it is necessary to solve the requirement of strong oxidants due to the large bond-dissociation energy (BDE) of the C-H bonds in methane and achieve suppression of overoxidation due to the smaller BDE of the C-H bond in methanol as the product. On the other hand, to efficiently perform CO2 reduction, proton-coupled electron transfer (PCET) processes are required since the reduction potential of CO2 becomes positive by using proton-coupled processes; however, under the acidic conditions required for PCET, hydrogen evolution by the reduction of protons becomes competitive with CO2 reduction. Thus, it is indispensable to develop efficient catalysts for selective CO2 reduction. Recently, we have developed efficient catalytic reactions toward the alleviation of the concerns mentioned above. Concerning CH4 oxidation, inspired by metalloenzymes that oxidize hydrophobic organic substrates, a hydrophobic second coordination sphere (SCS) was introduced to an FeII complex bearing a pentadentate N-heterocyclic carbene ligand, and the FeII complex was used as a catalyst for CH4 oxidation in aqueous media. Consequently, CH4 was efficiently and selectively oxidized to methanol with 83% selectivity and a turnover number of 500. In contrast, when methanol was used as a substrate for catalytic oxidation by the FeII complex, oxidation products were obtained in a negligible yield, which was comparable to that of the control experiment without the catalyst. Therefore, the hydrophobic SCS of the FeII complex can capture only hydrophobic substrates such as CH4 and release hydrophilic products such as methanol to the aqueous medium for suppressing overoxidation ("catch-and-release" mechanism). On the other hand, for photocatalytic CO2 reduction, we have developed NiII complexes with N2S2-chelating ligands as catalysts, which have been inspired by carbon monoxide dehydrogenase, and have also introduced a binding site of Lewis-acidic metal ions to the SCS of the Ni complex. When Mg2+ was applied as a moderate Lewis acid, a Mg2+-bound Ni catalyst allowed us to achieve remarkable enhancement of the photocatalytic CO2 reduction to afford CO as the product with over 99% selectivity and a quantum yield of 11.4%. Divalent metal ions besides Mg2+ also showed similar positive impacts on photocatalytic CO2 reduction, whereas monovalent metal ions exhibited almost no effects and trivalent metal ions exclusively promoted hydrogen evolution. In this Account, we highlight our recent progress in the catalytic manipulations of CH4 and CO2 as C1 resources.

Titanium-Immobilized Layered HUS-7 Silicate as a Catalyst for Photocatalytic CO2 Reduction.

Utilizing photocatalytic CO2 reduction presents a promising avenue for combating climate change and curbing greenhouse gas emissions. However, maximizing its potential hinges on the development of materials that not only enhance efficiency but also ensure process stability. Here, we introduce Hiroshima University Silicate-7 (HUS-7) with immobilized Ti species as a standout contender. Our study demonstrates the remarkable photocatalytic activity of HUS-7 in CO2 reduction, yielding substantially higher carbonaceous product yields compared to conventional titanium-based catalysts TS-1 and P25. Through thorough characterization, we elucidate that their boosted photocatalytic performance is attributed to the incorporation of isolated Ti species within the silica-based precursor, serving as potent photoinduced active sites. Moreover, our findings underscore the crucial role of the Ligand-to-Metal Charge Transfer (LMCT) process in facilitating the photoactivation of CO2 molecules, shedding new light on key mechanisms underlying photocatalytic CO2 reduction.

Highly active iron oxide@NC catalyst derived from the iron acetate/polyacrylonitrile threads: Driving nitroarene conversion to value‐added amines

AbstractChemoselective reduction of nitroarenes to corresponding arylamines is a significant reaction in the chemical industry. However, in the presence of other reducible groups, including halogenated nitrobenzene, nitrobiphenyl, and nitroquinoline in the same molecule of nitroaromatics, the control of chemoselectivity remains challenging. Here, a facile fabrication of a heterogeneous iron‐based catalyst is reported as a potential alternative to precious metal catalysts for the chemoselective reduction of nitroarenes. The pyrolysis of iron acetate/polyacrylonitrile (PAN) template under an inert atmosphere furnishes active Fe3O4 nanoparticles (NPs) encapsulated in nitrogen‐doped (N‐doped) carbon layers, which can provide more catalytic active sites (Fe3O4/PAN@800). Notably, non‐precious iron oxide NPs supported on N‐doped carbon support prevent aggregation, thereby enhancing the catalytic activity. The sustainable and reusable Fe3O4/PAN@800 catalyst, having only 0.8% metal content as demonstrated by x‐ray photoelectron spectroscopy, delivers excellent yields of corresponding amines from differently functionalized nitroarenes. Hydrogenation of a series of structurally functionalized nitroarenes produced excellent yields of anilines, which serve as building blocks and intermediates for fine and bulk chemicals. Hydrogenation of 2‐chloro‐3‐nitropyridine, 2‐nitro‐1,1′‐biphenyl, ortho‐nitroaniline, and 4‐aminophenyl acrylonitrile yielded respective anilines up to 99%. The active sites of Fe3O4 have magnetic performance, hence, the catalyst can be easily recovered using a magnet and reused for at least five cycles without significant loss of catalytic activity. Therefore, the easily prepared, cost‐effective, and reusable Fe3O4/PAN@800 catalyst presented in this study shows potential for applications in the selective reduction of aromatic nitro compounds. Consequently, this study potentially establishes a guideline for the facile preparation of abundant transition‐non‐noble metal‐based reusable supported catalysts for various applications in the chemical industry.

Mechanistic insight into electrocatalytic CO2 reduction to formate by the iron(I) porphyrin complex: A DFT study

Electrocatalytic reduction of CO2 into value-added chemicals has been considered as a promising pathway to mitigate the energy crisis and global warming. Iron porphyrins have been extensively studied for electrocatalytic CO2 reduction reaction (CO2RR), known for their ability to promote CO2-to-CO conversion. However, the mechanism of CO2-to-HCOO− conversion by Fe porphyrin remains unclear. Here, by means of density functional theory (DFT) calculations, we investigated the detailed mechanism of a novel Fe porphyrin catalyst for CO2 reduction to HCOO− in its Fe(I) state. Our results demonstrated that the reduction of CO2 to HCOO− proceeds via the C-protonation of an FeII-OCO•− complex, rather than through the hydrolysis of an FeIII-COOH complex or CO2 insertion in an Fe−H bond. Furthermore, the FeIII-COOH complex is found to be a unstable intermediate. Protonation of its hydroxyl group, accompanied by C−OH bond cleavage to produce CO, is both thermodynamically and kinetically unfeasible. Instead, the FeIII-COOH complex undergoes a coordination switch followed by a conformational change to form the active FeII-OCO•− complex, which promotes the production of HCOO−. Moreover, the single-electron reduction of FeIII-COOH gives FeII-COOH, leading to formation of CO rather than HCOO−. The insights gained from this study may contribute to design of electrocatalysts for selective CO2 reduction to formate.

High-Pressure nitrogen assisted synthesis of Small-Sized, Carbon-Encapsulated PtCo alloy nanoparticles as highly stable oxygen reduction catalysts

The development of small-sized platinum-based alloy catalysts with exceptional stability is crucial for the advancement of oxygen reduction reactions in fuel cells. Herein, we present a synthesis approach for fabricating small-sized carbon-encapsulated PtCo/C catalysts facilitated by high-pressure nitrogen during annealing. Remarkably, the resulting PtCo/C catalyst exhibits outstanding performance, showcasing minimal degradation (4.7%) in mass activity after enduring 30,000 cycles owing to its robust carbon-coating architecture.

Ultrafast Two-Color X-Ray Emission Spectroscopy Reveals Excited State Landscape in a Base Metal Dyad.

Effective photoinduced charge transfer makes molecular bimetallic assemblies attractive for applications as active light-induced proton reduction systems. Developing competitive base metal dyads is mandatory for a more sustainable future. However, the electron transfer mechanisms from the photosensitizer to the proton reduction catalyst in base metal dyads remain so far unexplored. A Fe─Co dyad that exhibits photocatalytic H2 production activity is studied using femtosecond X-ray emission spectroscopy, complemented by ultrafast optical spectroscopy and theoretical time-dependent DFT calculations, to understand the electronic and structural dynamics after photoexcitation and during the subsequent charge transfer process from the FeII photosensitizer to the cobaloxime catalyst. This novel approach enables the simultaneous measurement of the transient X-ray emission at the iron and cobalt K-edges in a two-color experiment. With this methodology, the excited state dynamics are correlated to the electron transfer processes, and evidence of the Fe→Co electron transfer as an initial step of proton reduction activity is unraveled.

High-Energy Polynitrogen N10 Stabilized on Multi-Walled Carbon Nanotubes.

The synthesis of stable polynitrogen compounds with high-energy density has long been a major challenge. The cyclo-pentazolate anion (cyclo-N5 -) is successfully converted into aromatic and structurally symmetric bipentazole (N10) via electrochemical synthesis using highly conductive multi-walled carbon nanotubes (MWCNTs) as the substrate and sodium pentazolate hydrate ([Na(H2O)(N5)]·2H2O) as the raw material. Attenuated total refraction Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and density functional theory calculations confirmed the structure and homogeneous distribution of N10 in the sidewalls of the MWCNTs (named MWCNT-N10-n m). The MWCNT-N10-2.0 m is further used as a catalyst for electrochemical oxygen reduction to synthesize hydrogen peroxide from oxygen with a two-electron selectivity of up to 95%.

Enhanced activity and water resistance of SiO2-coated Co/In-SSZ-13 catalysts in the selective catalytic reduction of NOx with CH4

CH4 selective catalytic reduction of NOx (CH4-SCR) is a promising technology to synergistic control of CH4 and NOx emission from LNG-powered vehicles and ships, while its insufficient catalytic activity and H2O resistance are key barriers for application. In this work, SiO2 coated Co3O4/In-SSZ-13 catalysts (Co/In-Z@Si) were prepared to simultaneously improve the CH4-SCR activity and H2O tolerance. The proper Co3O4 introduction enhanced the catalytic performance of the In-SSZ-13, while excessive amount of Co3O4 addition led to more CH4 being oxidized and insufficient CH4 participating in the CH4-SCR reaction. There was a “seesaw effect” between NO oxidation and CH4 oxidation performance of the catalysts. The H2O resistance of the Co/In-Z catalysts significantly enhanced via ultrathin SiO2 coating. The NOx and CH4 conversion maintained 81 % and 90 % in the presence of H2O at 500 °C for the Co/In-Z@Si catalyst, respectively. The in situ DRIFTS confirmed that the SiO2 coating could adsorb H2O molecules, prevent H2O from contacting the active sites, and limit the competitive adsorption between H2O and CH4 on the catalyst. This work provides a good candidate with superior catalytic performance and H2O resistance for removal of NOx and CH4 from LNG-powered vehicles and ships simultaneously.

Investigating the performance of CoFe2O4@TiO2 nanomaterial as multifunctional cathode catalyst for simultaneous dye degradation and oxygen reduction in microbial desalination cell

Microbial desalination cell (MDC) is an emerging technology in which water is desalinated and energy is generated by the breakdown of organic compounds and catalyzed by microorganisms using the potential gradient created in the reactor. MDC efficacy is substantially influenced by the oxygen reduction reaction (ORR) occurring at the cathode, albeit potential hindrances include sluggish reaction rates and biofouling development. The present study involved synthesizing and utilizing CoFe2O4@TiO2 nanocomposite as a multifunctional catalyst on a cathode surface for efficient ORR and dye removal. XPS, HRTEM, and XRD techniques were used to ascertain the NPs' morphology, surface properties, dimensions, and XRD patterns. Physicochemical investigation showed that the nanoparticles had a consistent distribution, a mean diameter of 18.11 nm, and a spherical shape. Researchers tested MDCs with nanoparticles (NPs). The highest power density was 4.56 W/m3, 50 % more than the MDC with a lower loading density. The desalination efficiency was found to be 60 % at 1.5 mg/cm2 CoFe2O4@TiO2, however, it was 80 and 81 % at 2.5 and 2.0 mg/cm2 catalyst concentrations, respectively. The dye degradation efficiency of as high as 88 % was observed with CoFe2O4@TiO2 nanocomposite cathode MDC. The findings show that CoFe2O4@TiO2 nanocomposite might be an economically feasible ORR catalyst, improving MDC efficiency and cost.