Operando Insights into Nanoparticle Transformations during Catalysis

Nanostructured materials play an important role in today’s chemical industry acting as catalysts in heterogeneous thermal and electrocatalytic processes for chemical energy conversion and the production of feedstock chemicals. Although catalysis research is a long standing discipline, the fundamental properties of heterogeneous catalysts like atomic structure, morphology and surface composition under realistic reaction conditions, together with insights into the nature of the catalytically active sites, have remained largely unknown. Having access to such information is however of outmost importance in order to understand the rate-determining processes and steps of many heterogeneous reactions and identify important structure-activity/selectivity relationships enabling knowledge-driven improvement of catalysts. In the last decades, in situ and operando methods have become available to identify the structural and morphological properties of the catalysts under working conditions. Such investigations have led to important insights into the catalytically-active state of the materials at different length scales, from the atomic level to the nano-/micrometer scale. The accessible operando methods utilizing photons range from vibrational spectroscopy in the infrared and optical regime to small-angle X-ray scattering (SAXS), diffraction (XRD), absorption spectroscopy (XAFS) and photoelectron spectroscopy (XPS), whereas electron-based techniques include scanning (SEM) and transmission microscopy (TEM) methods. In this work, we summarize recent findings of structural, morphological and chemical nanoparticle transformations during selected heterogeneous and electrochemical reactions, integrate them into the current state of knowledge, and discuss important future developments

Artificial Photosynthesis for Solar Fuels - an Evolving Research Field within AMPEA, a Joint Programme of the European Energy Research Alliance

On the path to an energy transition away from fossil fuels to sustainable sources, the European Union is for the moment keeping pace with the objectives of the Strategic Energy Technology-Plan. For this trend to continue after 2020, scientific breakthroughs must be achieved. One main objective is to produce solar fuels from solar energy and water in direct processes to accomplish the efficient storage of solar energy in a chemical form. This is a grand scientific challenge. One important approach to achieve this goal is Artificial Photosynthesis. The European Energy Research Alliance has launched the Joint Programme "Advanced Materials & Processes for Energy Applications” (AMPEA) to foster the role of basic science in Future Emerging Technologies. European researchers in artificial photosynthesis recently met at an AMPEA organized workshop to define common research strategies and milestones for the future. Through this work artificial photosynthesis became the first energy research sub-field to be organised into what is designated "an Application” within AMPEA. The ambition is to drive and accelerate solar fuels research into a powerful European field - in a shorter time and with a broader scope than possible for individual or national initiatives. Within AMPEA the Application Artificial Photosynthesis is inclusive and intended to bring together all European scientists in relevant fields. The goal is to set up a thorough and systematic programme of directed research, which by 2020 will have advanced to a point where commercially viable artificial photosynthetic devices will be under development in partnership with industr

Heterogeneous chemical reactions—A cornerstone in emission reduction of local pollutants and greenhouse gases

The current state and challenges of advanced experimental and modeling methods for a better understanding of heterogeneous chemical reactions are discussed using examples from developing and future technologies in the area of emission reduction of local pollutants and greenhouse gases. In situ and operando experimental techniques using laser and X-ray absorption spectroscopy, for instance, are able to resolve spatial and temporal concentration and temperature profiles in the near-wall gas phase, the interphase and inside the solid bulk. They have been exploited for a better understanding of the interaction of chemical reactions and transport processes. The experimental elucidation of chemical conversion on the microscopic scale leads to elementary step-like surface reaction mechanisms. The microkinetic description of gas-surface reactions is still challenging due to the complex influence of the modification of the solid material itself on the microscopic scale during the chemical reaction, which is caused by intrinsic materials’ modifications due to adsorbed species and temperature variations. Furthermore, transient inlet and boundary conditions on the reactor scale have a strong impact on the material and reaction rate. In addition to thermochemical reactions, an additional complexity comes into play with electrochemical ones. This paper will discuss heterogeneous chemical reactions in the light of emerging technologies such as emission control of natural gas and hydrogen fueled engines, use of CO$_{2}$ in chemical (methanation, dry reforming) and steel industry (off-gas reforming), hydrogen production by pyrolysis of methane, small-scale ammonia synthesis and use, and recyclable carbon-free energy carriers. Hence, this article will also reveal a new playground and the potential of methods, know-how, and skills of the combustion community to significantly contribute to the solution of climate-change relevant challenges

Faceted nanomaterial synthesis, characterizations and applications in reactive electrochemical membrane filtration

Facet engineering of nanomaterials, especially metals and metal oxides has become an important strategy for tuning catalytic properties and functions from heterogeneous catalysis to electrochemical catalysis, photocatalysis, biomedicine, fuel cells, and gas sensors. The catalytic properties are highly related to the surface electronic structures, surface electron transport characteristics, and active center structures of catalysts, which can be tailored by surface facet control. The aim of this doctoral dissertation research is to study the facet-dependent properties of metal or metal oxide nanoparticles using multiple advanced characterization techniques. Specifically, the novel atomic force microscope-scanning electrochemical microscope (AFM-SECM) and density functional theory (DFT) calculations were both applied to both experimentally and theoretically investigate facet dependent electrochemical properties, molecular adsorption, and dissolution properties of cuprous oxide and silver nanoparticles. To promote the facet engineered nanomaterials for environmental engineering apparitions, our research has evaluated the performances of electrochemically reactive membranes that were prepared with novel 2D nanomaterials with surface functioal modifications to enable electrochemical advanced oxidation processes (EAOPs) in membrane filtration process. Our results demonstrated many advantages such as tunable reactivity, tailored surface reactions, antifouling features, and feasibility of large-scale continuous operations. Specifically, this dissertation will introduce our electrochemical membrane synthesis, reactivity, aging, byproducts formation and electrochemical adsorption and desorption, oxidation of pollutants such as two typical per-and poly-fluoroalkyl substances (PFAS), perfluorooctanoic Acid (PFOA) and perfluorobutanoic acid (PFBA)

Recent advances in metallic glass nanostructures: synthesis strategies and electrocatalytic applications

Recent advances in metallic glass nanostructures (MGNs) are reported, covering a wide array of synthesis strategies, computational discovery, and design solutions that provide insight into distinct electrocatalytic applications. A brief introduction to the development and unique features of MGNs with an overview of top-down and bottom-up synthesis strategies is presented. Specifically, the morphology and structural analysis of several examples applying MGNs as electrodes are highlighted. Subsequently, a comprehensive discussion of commonly employed kinetic parameters and their connection with the unique material structures of MGNs on individual electrocatalytic reactions is made, including the hydrogen evolution reaction, oxygen reduction reaction, and alcohol (methanol or ethanol) oxidation reaction. Finally, a summary of the challenges and perspective on the future research and development relevant to MGNs as electrocatalysts is provided.317FAPESP – FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO2017/11958‐

Polymers and plastics modified electrodes for biosensors: a review

Polymer materials offer several advantages as supports of biosensing platforms in terms of flexibility, weight, conformability, portability, cost, disposability and scope for integration. The present study reviews the field of electrochemical biosensors fabricated on modified plastics and polymers, focusing the attention, in the first part, on modified conducting polymers to improve sensitivity, selectivity, biocompatibility and mechanical properties, whereas the second part is dedicated to modified “environmentally friendly” polymers to improve the electrical properties. These ecofriendly polymers are divided into three main classes: bioplastics made from natural sources, biodegradable plastics made from traditional petrochemicals and eco/recycled plastics, which are made from recycled plastic materials rather than from raw petrochemicals. Finally, flexible and wearable lab-on-a-chip (LOC) biosensing devices, based on plastic supports, are also discussed. This review is timely due to the significant advances achieved over the last few years in the area of electrochemical biosensors based on modified polymers and aims to direct the readers to emerging trends in this field.Peer ReviewedPostprint (published version

A review on exhaust gas after-treatment of lean-burn natural gas engines – From fundamentals to application

Modern lean-operated internal combustion engines running on natural gas, biogas or methane produced from wind or solar energy are highly fuel-efficient and can greatly contribute to securing energy supply, e.g. by mitigating fluctuations in the power grid. Although only comparably low emission levels form during combustion, a highly optimized emission control system is required that converts pollutants over a wide range of operation conditions. In this context, this review article pinpoints the main challenges during methane and formaldehyde oxidation as well as selective catalytic reduction of nitric oxides. The impact of catalyst formulation and operation conditions on catalytic activity and selectivity as well as the combination of several technologies for emission abatement is critically discussed. Additionally, recent experimental and theory-based progress and developments are assessed, allowing coverage of all time and length scales relevant in emission control, i.e. ranging from mechanistic and fundamental insights including atomic-level phenomena to full-scale applications

Nanoporous Gold: From Structure Evolution to Functional Properties in Catalysis and Electrochemistry

Nanoporous gold (NPG) is characterized by a bicontinuous network of nanometer-sized metallic struts and interconnected pores formed spontaneously by oxidative dissolution of the less noble element from gold alloys. The resulting material exhibits decent catalytic activity for low-temperature, aerobic total as well as partial oxidation reactions, the oxidative coupling of methanol to methyl formate being the prototypical example. This review not only provides a critical discussion of ways to tune the morphology and composition of this material and its implication for catalysis and electrocatalysis, but will also exemplarily review the current mechanistic understanding of the partial oxidation of methanol using information from quantum chemical studies, model studies on single-crystal surfaces, gas phase catalysis, aerobic liquid phase oxidation, and electrocatalysis. In this respect, a particular focus will be on mechanistic aspects not well understood, yet. Apart from the mechanistic aspects of catalysis, best practice examples with respect to material preparation and characterization will be discussed. These can improve the reproducibility of the materials property such as the catalytic activity and selectivity as well as the scope of reactions being identified as the main challenges for a broader application of NPG in target-oriented organic synthesis

Highly Ordered Titanium and Titanium Dioxide Nanotubes Electrode Development and Electrochemical Application

Titanium dioxide (TiO2) is one of the most extensively studied compounds in materials science. Since the first successful fabrication of highly ordered TiO2 nanotubes (TiO2-NTs) arrays via electrochemical anodization in ’90s, thousands of publications have focused on the growth, properties, and applications of these versatile nanostructures. In the present study, anodization conditions were found to be the key determinants for TiO2-NTs’ structures and properties. In fact, this work demonstrates that tuning anodization conditions leads to tailoring TiO2-NTs’ for distinctive electrochemical applications. Deconvoluting myriad factors, for example temperature, electrolyte, reaction time, and potential, which govern the anodized products properties, was possible by examining the correlation anodization parameters to TiO2-NTs characteristics. In present study, a synergistic experimental approach was employed in order to investigate how anodization parameters affect the anodized products structures and properties. This work clearly delineates that the nanoscale geometry (tube diameter, surface area, and self-ordering degree) of TiO2-NTs is highly tailorable by tuning the anodization parameters. Upon achieving well-controlled TiO2-NTs, they exhibited good electrosorption capacity and selectivity in the alkaline metal ions electrosorption test. In addition, a novel strategy to fabricate hierarchically flow-through 3D Ti/TiO2 NT electrodes for hydrogen evolution reaction (HER) was developed. The 3D Ti/TiO2 NT electrodes reported here take advantage of 3D printing and in-situ anodization to achieve efficient HER electrocatalysis. Most importantly, the preparation of the 3D Ti/TiO2 NT electrode is facile and readily scalable since the fabrication does not include time- and energy-consuming processes such as complex precursor preparation and high-temperature heat treatments. The large-scale construction of 3D Ti/TiO2 NT does not require high capital cost and the flow-through feature makes it very appealing for continuous, industrial- scale hydrogen production. This study also provides evidence that the TiO2 NT on the surface of the 3D Ti templates is the active catalytic surface promoting HER, by a two-step mechanism that contributes to the faster rate of the overall process. The 3D Ti templates contribute to fast HER reaction rates in terms of offering a seamless electron transfer network and large exposed active sites, namely TiO2 NT

Pressurized CO2 Electrochemical Conversion to Formic Acid: From Theoretical Model to Experimental Results

To curb the severely rising levels of carbon dioxide in the atmosphere, new approaches to capture and utilize this greenhouse gas are currently being investigated. In the last few years, many researches have focused on the electrochemical conversion of CO2 to added-value products in aqueous electrolyte solutions. In this backdrop, the pressurized electroreduction of CO2 can be assumed an up-and-coming alternative process for the production of valuable organic chemicals [1-3]. In this work, the process was studied in an undivided cell with tin cathode in order to produce formic acid and develop a theoretical model, predicting the effect of several operative parameters. The model is based on the cathodic conversion of pressurized CO2 to HCOOH and it also accounts for its anodic oxidation. In particular, the electrochemical reduction of CO2 to formic acid was performed in pressurized filter press cell with a continuous recirculation of electrolytic solution (0.9 L) at a tin cathode (9 cm2) for a long time (charge passed 67’000 C). It was shown that it is possible to scale-up the process by maintaining good results in terms of faradaic efficiency and generating significantly high concentrations of HCOOH (about 0.4 M) [4]. It was also demonstrated that, for pressurized systems, the process is under the mixed kinetic control of mass transfer of CO2 and the reduction of adsorbed CO2 (described by the Langmuir equation), following our proposed reaction mechanism [5]. Moreover, the theoretical model is in good agreement with the experimental results collected and well describes the effect of several operating parameters, including current density, pressure, and the type of reactor used. 1. Ma, S., & Kenis, P. J. (2013). Electrochemical conversion of CO2 to useful chemicals: current status, remaining challenges, and future opportunities. Current Opinion in Chemical Engineering, 2(2), 191-199. 2. Endrődi, B., Bencsik, G., Darvas, F., Jones, R., Rajeshwar, K., & Janáky, C. (2017). Continuous-flow electroreduction of carbon dioxide. Progress in Energy and Combustion Science, 62, 133-154. 3. Dufek, E. J., Lister, T. E., Stone, S. G., & McIlwain, M. E. (2012). Operation of a pressurized system for continuous reduction of CO2. Journal of The Electrochemical Society, 159(9), F514-F517. 4. Proietto, F., Schiavo, B., Galia, A., & Scialdone, O. (2018). Electrochemical conversion of CO2 to HCOOH at tin cathode in a pressurized undivided filter-press cell. Electrochimica Acta, 277, 30-40. 5. Proietto, F., Galia, A., & Scialdone, O. (2019) Electrochemical conversion of CO2 to HCOOH at tin cathode: development of a theoretical model and comparison with experimental results. ChemElectroChem, 6, 162-172