Graphene supported heterogeneous catalysts: An overview

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The World's energy consumption has increased drastically over the past several decades, particularly driven by increasing population and economic activities as well as rising living standards with technological advancements. Since the industrial revolution, fossil fuels have been the major source of energy productions, which is today shown as the primary cause of the ongoing climate change and associated environmental challenges in threatening the existence of many living species and human life and comfort. According to the statistics provided by International Energy Agency (IEA),1 the global energy supply was 14 282 Mtoe in 2018 that is 115% higher than that of the value for 1973. Fossil fuels, such as natural gas, coal and oil are still playing a critical role and covering more than 80% of global energy demands. The concerns associated with global warming and depletion of energy sources have been directing the attention to renewable and environmentally-benign energy solutions. However, efficient, affordable, and nature-friendly energy storage systems are the key to using renewable energy sources effectively. In this study, a comprehensive literature search is conducted to study and bibliografically evalute Canada's energy storage research and development activities over the last five decades. The present study intends to present the cumulative picture on energy storage reseach and development efforts and assess how universities, research institutes and funding agencies have contributed to this particular field. The literature search compiles a total of fifty-year data on energy storage-related research and development activities conducted in Canada. The number of conducted studies associated with energy storage regarding research articles, books, research projects, dissertations, and patents is presented in the period from 1971 to 2021. Furthermore, the Canadian institutes are ranked based on their scholarly ouputs and publications to indicate the most productive ones in the field of energy storage based on the data presented in the literature sources. Energy storage is described as the capture of harvested energy for later use to maintain the balance fluctuations between energy demand and supply. As the world moves towards a low-carbon economy, energy storage systems are exepcted to even play a more critical role in extracting more energy from renewable resources.10 The intermittent characteristic of renewable resources, specifically solar and wind, is one of the major challenges ahead of a reliable and steady renewable energy supply. This can be avoided by storing excess energy to re-use when the renewable resources are not sufficient or unavailable. Energy storage systems can be categorized in different ways in regards to the form of converted and stored energy. Figure 1 presents an overview of energy storage system categories which are considered in this study. It is important to note that chemical energy storage allows to storage and transportation of large amounts of energy for long distances with minimal self-discharge rates, which is crucial for the distribution and effective use of renewable energy resources. Figure 2 presents the energy density of various chemical fuels and batteries. Despite possessing high energy density, environmental concerns associated with the production and consumption of fossil-based chemical fuels, e.g. diesel, gasoline or natural gas, should be adrressed. In regards to nature-friendly chemical energy storage, particularly power-to-gas chemical storage, hydrogen is attracting favorable attention nowadays. In this regard, hydrogen appears to be the lightest and most abundant chemical element in the universe, but is not available freely (by itself). However, it occurs naturally within a compound such as water (H2O); therefore, it is an intermediate energy form. Excess electricity from renewables can be utilized in hydrogen production processes, i.e. electrolysis of water, to store energy in chemical form. Power-to-hydrogen chemical energy storage is a unique and clean method, and it can be compatible with electrochemical storage since hydrogen possesses much greater energy content. One of the major challenges with hydrogen is the low calorific value per unit of volume (MJ/m3) due to its low density. This can be avoided by deploying alternative hydrogen carriers, such as ammonia. Liquefaction at atmospheric conditions, high hydrogen atom content and high energy density characteristics make ammonia a favorable medium for storage and transportation of energy. It is further to note that batteries and capacitors are devices allowing electrochemical storage of electricity. The potential energy is stored in chemical form in batteries, while capacitors are expected to store their potential energy in the form of an electric field.14 Batteries are thus most commonly used and matured options that propose high energy densities and voltages. Lithium-ion (Li-ion), sodium-sulphur (NaS), nickel-cadmium (NiCd), lead acid (Pb-acid), lead-carbon batteries, zebra batteries (Na-NiCl2) and flow batteries are the existing battery types used in various applications. Due to their high specific energy (per unit weight) and high specific energy (per unit volume), lithium batteries attract considerable attention in electrical energy storage. Capacitors can be classified as electrostatic capacitors, electrolytic capacitors, and electrochemical capacitors, among which electrochemical, so-called supercapacitors, promote the highest capacitance per unit of volume owing to a porous structure 15. As a mechanical energy storage method, pumped hydro accounts for more than 95% of the global installed energy storage capacity.15 The main advantage of mechanical energy storage is to readily deliver energy. The method is easy to adapt for conversion and storage of energy from various sourcessuch as water current, wave, or tidal. Pumped hydro, compressed air, and flywheel are the commonly practiced mechanical energy storage methods. Pumped hydro and compressed air are bound to specific geographical characteristics, which is the main restriction for the implementation of these energy storage methods. A flywheel stores the energy obtained from a rotor mass spinning at very high speeds as kinetic energy. The stored kinetic energy can be later used to produce electricity by altering the angular velocity of the flywheel through a decelerating torque and using an electric motor in reverse 16. Despite of being non-suitable for long-term energy storage, flywheels offer favorable advantages, that is, long-life spin, high energy densities and low maintenance costs, and fast charging.17 Thermal energy storage (TES) systems are effective systems to store heat in a reservoir for a period of time (defined or undefined) for later use, that is, space heating and cooling, electricity production, hot water. If the reservoir temperature is kept under the atmospheric temperature, the storage process is called cold thermal energy storage.18 Operating temperature range, capacity requirements, charging and discharging requirements are some of important parameters when choosing an appropriate TES system for a desired application. Since the major proportion of produced and consumed energy is heat around the world, TES systems carries a significant weight regarding the development of effective energy systems . Furthermore, energy losses from the systems commonly occur in the form of heat. Decreasing losses via further utilizing from waste energy is one of many way to mitigate environmental impacts, which can be accomplished by implementing TES systems in a cost effective manner. In the current study, an overview of Canada's energy storage related studies from 1971 to 2021 is presented. The scope of this study is to present the contributions of Canadian universities, research institutes and funders to energy storage research and development efforts over the last five decades. The keywords and methodology that are used for the literature search are depicted in Figure 3. The collected and compiled data for the corresponding fields are presented in figures, and results are discussed in the following sections. In this study, an online literature search is conducted on Canada's energy storage related studies over the last five decades. The current section presents collected and compiled data in charts. The findings of the conducted study are discussed in detail. The most productive institutes of Canada regarding conducting or sponsoring energy storage-related studies are presented. The documents associated with energy storage in all subject areas are presented in Figure 4. In this regard, the highest number of energy storage-related studies were conducted in the subject area of engineering in Canada from 1971 to 2021. The fields of energy and chemistry appear as the other two major subject areas in which high number of energy storage research was conducted. While compiling data, attention has been paid to any potential field conflicts concerning the multi attribution of interdisciplinary publications. Therefore, it should be noticed that chemistry may have an impact on the subject areas of biochemistry, genetics, and molecular biology. The same impact of engineering could be seen on the subject area of energy. The data collected and analysed for comparative evaluation reveals that the Canadian institutes have produced 37 386 energy storage-related academic research publications over the last 50-year period. In this regard, Figure 5A presents the breakdown of energy storage-related publications affiliated to Canada in the corresponding material types in accordance with the publication years. Figure 5A shows that studies in this field consistently increases every year. Consequently, the year 2020 appears as the most productive one in this regard as of April 2021. In the light of this trendline, predicting that the year 2021 will be more productive than 2020 would not be wrong. Figure 5B has been prepared as a heat map to show Canada's provinces where energy storage-related studies were conducted over the last 50 years. In this regard, Ontario appears as the most productive province of Canada in terms of scholarly publications. However, one has to keep in mind that Ontario has the highest number of contributing institutes/universities compared to the rest of the provinces in Canada. Figure 6 presents the breakdown of the number of energy storage-related books, book chapters, and editorials in accordance with publication years in Canada. The year 2018 was the most productive year of Canada by producing 200 documents in the corresponding classification. The other important point that should be pinned in the figure is the year 2005. Compared to the previous year, almost five times more energy storage-related books were published in 2005. Compared to 2019, the number of published books decreased almost by half in 2020. The impact of COVID-19 is recognized as one of numerous reasons behind this result. The number of energy storage-related dissertations completed in Canada over the last five decades is primarily searched through and collected from Library and Archives Canada. The search results are, in this regard, presented in Figure 7. It can be noted that the data presented in Figure 7 is based on the number of energy storage-related theses available in the library; and thus, the results are subject to change in accordance with instantaneous new data entry to the library. As of April 2021, there are 626 energy storage-related MSc and PhD theses/dissertations entered in the online system of Library and Archives Canada. The highest number of theses/dissertations was recorded in the year of 2013 with a value of 62. Based on data collected from the website of Canadian Intellectual Property Office, the number of energy storage-related patents of Canada is 11 719 for the last 50 years. The corresponding results are presented Figure 8. According to this, the year of 2018 appeared to be the Canada's most productive year in terms of patents registered under the title of energy storage. Canada is blessed with institutions that have been supporting energy storage-related research and developments by providing funds. Over the evaluated period of 50 years, the Natural Sciences and Engineering Research Council of Canada (NSERC) appears as the major funding agency for Canada's energy storage related research, development, partnership, strategic innovation and commercialization efforts and has supported more than 8500 projects in the field of energy storage. A total number of projects that have been funded by Canadian institutes have become 18021 from 1971 to 2021. It is most likely to observe a major increase in the number of projects by the impact of the recent hydrogen strategic plan of Canada. Being an excellent energy storage medium is one of many advantages of hydrogen. Therefore, there is a significant correlation in between hydrogen and energy storage research efforts. The subject matter report is already named as call-to-action for green hydrogen transition for the energy sector. In the report, the importance of dedicating more domestic resources to green hydrogen efforts to achieve the targets by 2050 is emphasized clearly (Figure 9). The development and implementation efforts of effective, affordable, and nature-friendly energy storage systems are recognized as a key requirement in achieving a green energy transition. In this regard, Canada intends to be the country leading and inspiring many others. Figure 10 shows the a number of Canadian institutes/universities that have produced more than 100 scholarly publications on energy storage under the subject area of energy. According to this, the total number of such scholarly publications has been 9125 over the past five decades. The results clearly show that there are two universities, such as University of Waterloo with 809 publications and Ontario Tech. University (formerly University of Ontario Institute of Technology) with 697 publications, leading in this particular area. University of Waterloo appears as the most productive Canadian university with a total number of 809 publications while Ontario Tech. University, which is one of the Canada's youngest universities, follows with a total number of 697 publications. The specific affiliations in the publications show that the researchers working in the productive environment of Clean Energy Research Laboratory (CERL) at Ontario Tech. have played a major role in this achievement. The data that support the findings of this study are available in Scopus, Library and Archives Canada and Canadian Intellectual Property Office with the reference number of [17], [18], and [19], respectively. These data were derived from the following resources available in the public domain: https://www.scopus.com/search/form.uri?display=basic&zone=header&origin, https://www.bac-lac.gc.ca/eng/services/theses/Pages/search.aspx, https://www.ic.gc.ca/opic-cipo/cpd/eng/search/basic.html?wt_src=cipo-patent-main.

A ligand-recyclable, environmentally benign heterogeneous catalyst system composed of CuI and polystyrene-supported N(-(4-(aminomethyl)naphthalen-1-yl)-N(-phenyl-1H-pyrrole-2-carbohydrazide (PSAP) has been established for Ullmann type C–N coupling based on the homogeneous catalyst system N′,N′-diphenyl-1H-pyrrole-2-carbohydrazide/CuI. This heterogeneous catalyst system maintained the catalytic effectiveness of the homogeneous catalyst. A variety of functionalized aryl bromides can be efficiently aminated with aryl amines and aliphatic amines with high selectivity for amines over alcohols. Moreover, a practical application of this catalyst system to promote the reaction of commercially available 4-methoxy-2-methylaniline and bromobenzene in 10 mmol scale, provided 2-methyl-4-methoxydiphenylamine (MMDPA) with 93% yield with the merit of the approach being simple operation for work-up and purification.

Homogeneous copolymerization of styrene and 1‐hexene was carried out in toluene at room temperature using bisindenyl ethane zirconium dichloride/methylaluminoxane (MAO). The supported catalyst was prepared with immobilization of Et(Ind)2ZrCl2/MAO on silica (calcinated at 500°C) with premixed method. Heterogeneous copolymerization of styrene/1‐hexene with different mole ratios was carried out in the presence of supported catalyst system. The copolymers obtained from homogeneous and heterogeneous catalyst system were characterized by 1H NMR and 13C NMR. Composition of the resulting copolymers was determined by 1H NMR data. Analysis of 13C NMR spectra of obtained copolymers by homogeneous and heterogeneous catalyst systems present isotactic olefin‐enriched copolymers. Molecular weight and thermal behavior of resulting copolymers was investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4008–4014, 2007

Immobilized Pd on a NHC-functionalized metal-organic FrameworkMIL-101(Cr): An efficient heterogeneous catalyst in the heck and copper-free Sonogashira coupling reactions

Abstract3‐Ethynylthiophene (3ETh) was polymerized with Rh(I) complexes: [Rh(cod)acac], [Rh(nbd)acac], [Rh(cod)Cl]2, and [Rh(nbd)Cl]2 (cod is η2:η2‐cycloocta‐1,5‐diene and nbd η2:η2‐norborna‐2,5‐diene), used as homogeneous catalysts and with the last two complexes anchored on mesoporous polybenzimidazole (PBI) beads: [Rh(cod)Cl]2/PBI and [Rh(nbd)Cl]2/PBI used as heterogeneous catalysts. All tested catalyst systems give high‐cis poly(3ETh). In situ NMR study of homogeneous polymerizations induced with [Rh(cod)acac] and [Rh(nbd)acac] complexes has revealed: (i) a transformation of acac ligands into free acetylacetone (Hacac) occurring since the early stage of polymerization, which suggests that this reaction is part of the initiation, (ii) that the initiation is rather slow in both of these polymerization systems, and (iii) a release of cod ligand from [Rh(cod)acac] complex but no release of nbd ligand from [Rh(nbd)acac] complex during the polymerization. The stability of diene ligand binding to Rh‐atom in [Rh(diene)acac] catalysts remarkably affects only the molecular weight but not the yield of poly(3ETh). The heterogeneous catalyst systems also provide high‐cis poly(3ETh), which is of very low contamination with catalyst residues since a leaching of anchored Rh complexes is negligible. The course of heterogeneous polymerizations is somewhat affected by limitations arising from the diffusion of monomer inside catalyst beads. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2776–2787, 2008

Multi-scenario design of ammonia-based energy storage systems for use as non-wires alternatives

Catalysis, particularly heterogeneous catalysis, is crucial in the chemical industry and energy storage. Approximately 80% of all chemical products produced by heterogeneous catalysis are produced by solid catalysts, which are essential for the synthesis of ammonia, methanol, and hydrocarbons. Despite extensive use, challenges in catalyst development remain, including enhancing selectivity, stability, and activity. These effective properties are influenced by the nanoscale morphology of the catalysts, whereby the size of the nanoparticles is only one key descriptor. To investigate the relationship between nanoparticle morphology and catalytic performance, a comprehensive 3D analysis of nano-scale catalyst particles is necessary. However, traditional imaging techniques for a representative recording of this size range, such as transmission electron microscopy (TEM), are mostly limited to 2D. Thus, in the present paper, a stochastic 3D model is developed for a data-driven analysis of the nanostructure of catalyst particles. The calibration of this model is achieved using 2D TEM data from two different length scales, allowing for a statistically representative 3D modeling of catalyst particles. Furthermore, digital twins of catalyst particles can be drawn for the stochastic 3D model for virtual materials testing, enhancing the understanding of the relationship between catalyst nanostructure and performance.

Gold standard support! The direct reductive mono- or di-N-alkylation of aromatic nitro compounds with alcohols, using a hydrogen-borrowing strategy, was efficiently promoted by a ligand-free titania-supported gold catalyst system (see scheme). A variety of nitroarenes were selectively converted into the corresponding secondary or tertiary amines in good to excellent yields without any co-catalysts, such as bases and stabilizing ligands. Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Laser-induced fluorescence detection is one of the most sensitive detection techniques and it has found enormous applications in various areas. The purpose of this research was to develop detection approaches based on laser-induced fluorescence detection in two different areas, heterogeneous catalysts screening and single cell study. First, we introduced laser-induced imaging (LIFI) as a high-throughput screening technique for heterogeneous catalysts to explore the use of this high-throughput screening technique in discovery and study of various heterogeneous catalyst systems. This scheme is based on the fact that the creation or the destruction of chemical bonds alters the fluorescence properties of suitably designed molecules. By irradiating the region immediately above the catalytic surface with a laser, the fluorescence intensity of a selected product or reactant can be imaged by a charge-coupled device (CCD) camera to follow the catalytic activity as a function of time and space. By screening the catalytic activity of vanadium pentoxide catalysts in oxidation of naphthalene, we demonstrated LIFI has good detection performance and the spatial and temporal resolution needed for high-throughput screening of heterogeneous catalysts. The sample packing density can reach up to 250 x 250 subunits/cm2 for 40-μm wells. This experimental set-up also can screen solid catalysts via near infrared thermography detection.

Laser-induced fluorescence detection is one of the most sensitive detection techniques and it has found enormous applications in various areas. The purpose of this research was to develop detection approaches based on laser-induced fluorescence detection in two different areas, heterogeneous catalysts screening and single cell study. First, the author introduced laser-induced imaging (LIFI) as a high-throughput screening technique for heterogeneous catalysts to explore the use of this high-throughput screening technique in discovery and study of various heterogeneous catalyst systems. This scheme is based on the fact that the creation or the destruction of chemical bonds alters the fluorescence properties of suitably designed molecules. By irradiating the region immediately above the catalytic surface with a laser, the fluorescence intensity of a selected product or reactant can be imaged by a charge-coupled device (CCD) camera to follow the catalytic activity as a function of time and space. By screening the catalytic activity of vanadium pentoxide catalysts in oxidation of naphthalene, they demonstrated LIFI has good detection performance and the spatial and temporal resolution needed for high-throughput screening of heterogeneous catalysts. The sample packing density can reach up to 250 x 250 subunits/cm2 for 40-μm wells. This experimental set-up also can screen solid catalysts via near infrared thermography detection. In the second part of this dissertation, the author used laser-induced native fluorescence coupled with capillary electrophoresis (LINF-CE) and microscope imaging to study the single cell degranulation. On the basis of good temporal correlation with events observed through an optical microscope, they have identified individual peaks in the fluorescence electropherograms as serotonin released from the granular core on contact with the surrounding fluid.

The cometathesis reaction of methyl oleate (MO) with unsaturated dicarboxylic acid esters has been studied using either a homogeneous catalyst system (WCl6‐Me4Sn) or a heterogeneous catalyst system (Re2O3‐Al2O3‐Me4Sn). In the presence of the homogeneous catalyst, dimethyl‐3‐hexenedioate (DMHD) reacted with MO to give cometathesis products in 47% yield with a distribution of products that agreed with the theoretical equilibrium composition. When dipropyl‐4‐octenedioate (DPOD) was used, however, the yield of cometathesis products was less than 1%. The lower reactivity of DPOD might be due to the formation of a stable complex of DPOD with the catalyst. The cometathesis reaction of MO and DMHD was also catalyzed by the heterogeneous catalyst. However, the reaction rate decreased significantly and the distribution of products did not attain the theoretical. Similar results were obtained in the cometathesis reaction of MO and DPOD catalyzed by the heterogeneous catalyst. These results suggest that MO and DMHD are preferentially adsorbed onto the surface of this catalyst according to their polarity, and that the molar ratio of MO and DMHD at the catalytic site was different from that in the reaction medium.

Devices or physical media can store some form of energy to perform a useful operation at a later time or at a different location. Energy storage reduces mismatches between the energy production and demand. For example, solar energy if stored would still be available during the night. Also, the stored energy may be a supplement during the peak demand for energy. Besides, stored energy can be transported. A battery, for example, makes it possible to use a wrist watch, a mobile phone, or a laptop computer. This chapter begins by underlying the importance of energy storage and regulation by water and hydrogen and later discusses thermal, electric, chemical, and mechanical energy storage systems. Solar energy storage by sensible and/or latent heat and for short- and long-term applications is discussed briefly. Some common phase changing materials and their usage for the latent heat storage technique are described. Underground thermal energy systems are discussed briefly. Capacitor, hydroelectric, and battery are discussed for storing electricity. Chemical energy storage by biosynthesis is briefly discussed. Later, mechanical energy storage by compressed air, flywheel, hydraulic, and springs are discussed. There are 6 example problems and 35 practice problems at the end of the chapter.

Devices or physical media can store some form of energy to perform a useful operation later and/or at a different location. Energy storage reduces the mismatches between the energy production and demand. For example, if it is stored the solar energy would still be available during the night. Also, the stored energy may be a supplement during the peak demand for energy. Besides, a stored energy can be transported. A battery, for example, makes it possible to use a wristwatch, mobile phone, or a laptop computer. This chapter begins by underlying the importance of energy storage and regulation by water and hydrogen and later discusses thermal, electric, chemical, and mechanical energy storage systems. Solar energy storage by sensible and/or latent heat and for short- and long-term applications is discussed briefly. Some common phase changing materials and usage of them for the latent heat storage technique are described. Underground thermal energy systems are discussed briefly. Capacitor, hydroelectric, and battery are discussed in storing electricity. Chemical energy storage by biosynthesis is briefly discussed. Later, mechanical energy storage by compressed air, flywheel, hydraulic, and springs are discussed.

Controlled Assembly of Hierarchical Metal Catalysts with Enhanced Performances