Production Of Commodity Chemicals Research Articles

A thermostable calcium-based metal–organic framework for efficient capture and separation of acetylene from ternary mixture

High-efficiency and eco-friendly selective separation of C2H2 from industrial gaseous mixtures such as CO2 and CH4 is of great importance in the purification and production of downstream commodity chemicals. Herein, we report a thermostable calcium-based metal–organic framework, namely NUM-20, which could preferentially capture C2H2 from C2H2-containing gaseous mixtures. NUM-20 exhibits a higher capacity and preferential adsorption behavior of C2H2 versus the competing gases including CO2 and CH4, as reflected by single component gas sorption isotherms and the heat of adsorption. The IAST selectivity calculations indicate that NUM-20 possesses multiple component separation capacity, and the transient breakthrough simulations were performed to validate the capture and separation of C2H2 from multiple components. Furthermore, computational simulations were carried out to unveil the host–guest interactions under the molecular-level. This study on Ca-based MOF materials will enrich the three-dimensional Ca-based MOF adsorbents for gas capture and separation applications and address the industrial challenging separation process.

Shifts in catalyst deactivation mechanisms as a function of surface coverage during Friedel-Crafts acylation in zeolites

The production of commodity chemicals from renewable resources is often accompanied by rapid catalyst deactivation rates. An important example is direct Friedel Crafts acylation, which can yield a range of valuable products from surfactants to renewable transportation fuels. Furanic acyl acceptors are among the most intriguing and promising possible acceptors; however, they undergo self-coupling reactions in the presence of Brønsted acid surface sites leading to rapid catalyst deactivation. In this contribution, we study 2-methylfuran acylation with acetic acid over HZSM-5 catalysts at temperatures ranging from 160 to 240 °C, revealing the remarkable shift in deactivation behavior as a function of surface coverage of acetic acid. We reveal that a surface saturated with acetic acid lowers the deactivation rate by blocking the direct access of furanic species to surface sites. However, on surfaces fully saturated with carboxylic acids, deactivation is revealed to proceed via reactions between adsorbed products with gas phase methylfuran reactants.

Production of Value-Added Products as Food Ingredients via Microbial Fermentation

Humankind has been unknowingly utilizing food fermentations since the first creation of bread, cheese, and other basic foods. Since the beginning of the last century, microbial fermentation has been extensively utilized for production of commodity chemicals. It has also gained substantial interest in recent decades due to its underlying applications in the preparation of natural and safe food ingredients including enzymes, antimicrobial agents, vitamins, organic acids, sweeteners, stabilizers, emulsifiers, oligosaccharides, amino acids, and thickening agents. In addition, some novel food ingredients that were conventionally made from some other sources such as plant tissue cultures or animals are now being introduced in the industry as ‘fermentation products.’ Some examples of such novel fermentation food ingredients include flavonoids, cultured meat products, food colorants, antioxidants, lipids, and fatty acids. This review summarizes some of the most prominent food ingredients and novel fermentation food products currently being produced via microbial fermentation as well as the strategies to enhance such fermentation processes. Additionally, economical feedstocks are discussed with their potential to be converted into value-added products with the help of microbial fermentations.

Redox-Paired Alkene Difunctionalization Enables Skeletally Divergent Synthesis.

Multistep organic synthesis enables conversion of simple chemical feedstocks into a more structurally complex product that serves a particular function. The target compound is forged over several steps, with concomitant generation of byproducts in each step to account for underlying mechanistic features of the reactions (e.g., redox processes). To map structure-function relationships, libraries of molecules are often needed, and these are typically prepared by iterating an established multistep synthetic sequence. An underdeveloped approach is designing organic reactions that generate multiple valuable products with different carbogenic skeletons in a single synthetic operation. Taking inspiration from paired electrosynthesis processes that are widely used in commodity chemical production (e.g., conversion of glucose to sorbitol and gluconic acid), we report a palladium-catalyzed reaction that converts a single alkene starting material into two skeletally distinct products in a single operation through a series of carbon-carbon and carbon-heteroatom bond-forming events enabled by mutual oxidation and reduction, a process that we term redox-paired alkene difunctionalization. We demonstrate the scope of the method in enabling simultaneous access to reductively 1,2-diarylated and oxidatively [3 + 2]-annulated products, and we explore the mechanistic details of this unique catalytic system using a combination of experimental techniques and density functional theory (DFT). The results described herein establish a distinct approach to small-molecule library synthesis that can increase the rate of compound production. Furthermore, these findings demonstrate how a single transition-metal catalyst can mediate a sophisticated redox-paired process through multiple pathway-selective events along the catalytic cycle.

Co-doped hydroxyapatite as photothermal catalyst for selective CO2 hydrogenation

The rational design and in deep understanding of efficient, affordable and stable materials to promote the light-assisted production of fuels and commodity chemicals is very appealing for energy crisis and climate change amelioration. Herein, we have prepared a series of Co-doped hydroxyapatite (HAP) catalysts with different Co content. The materials structure has been widely investigated by XRD, FT-IR, HRTEM, XPS, XAS, as well as computational simulations based on Density Functional Theory (DFT) with PBE functional. At low Co loading, there is a partial substitution of Ca cations in the HAP structure, while higher loadings promote the precipitation of small (∼ 2 nm) Co nanoparticles on the HAP surface. For the optimal Co content, a constant CO rate of 62 mmol·g−1·h−1 at 1 sun illumination and 400 °C, with the material being stable for 90 h. Visible and NIR photons have been determined responsible of the light-assisted activity enhanced. Mechanistic studies based on both experimental and DFT simulations show that H2 preferentially adsorbs to metallic Co, while CO2 adsorbs to the HAP surface oxygen. Moreover, both direct photo- and plasmon-driven contributions have been separated in order to study their mechanisms independently.

Enhanced hybrid photocatalytic dry reforming using a phosphated Ni-CeO2 nanorod heterostructure

Operating the dry reforming reaction photocatalytically presents an opportunity to produce commodity chemicals from two greenhouse gases, carbon dioxide and methane, however, the top-performing photocatalysts presented in the academic literature invariably rely on the use of precious metals. In this work, we demonstrate enhanced photocatalytic dry reforming performance through surface basicity modulation of a Ni-CeO2 photocatalyst by selectively phosphating the surface of the CeO2 nanorod support. An optimum phosphate content is observed, which leads to little photoactivity loss and carbon deposition over a 50-hour reaction period. The enhanced activity is attributed to the Lewis basic properties of the PO43− groups which improve CO2 adsorption and facilitate the formation of small nickel metal clusters on the support surface, as well as the mechanical stability of CePO4. A hybrid photochemical-photothermal reaction mechanism is demonstrated by analyzing the wavelength-dependent photocatalytic activities. The activities, turnover numbers, quantum efficiencies, and energy efficiencies are shown to be on par with other dry-reforming photocatalysts that use noble metals, representing a step forward in understanding how to stabilize ignoble nickel-based dry reforming photocatalysts. The challenges associated with comparing the performance of photocatalysts reported in the academic literature are also commented on.

Analysis of the Scale of Global Human Needs and Opportunities for Sustainable Catalytic Technologies

We analyzed the enormous scale of global human needs, their carbon footprint, and how they are connected to energy availability. We established that most challenges related to resource security and sustainability can be solved by providing distributed, affordable, and clean energy. Catalyzed chemical transformations powered by renewable electricity are emerging successor technologies that have the potential to replace fossil fuels without sacrificing the wellbeing of humans. We highlighted the technical, economic, and societal advantages and drawbacks of short- to medium-term decarbonization solutions to gauge their practicability, economic feasibility, and likelihood for widespread acceptance on a global scale. We detailed catalysis solutions that enhance sustainability, along with strategies for catalyst and process development, frontiers, challenges, and limitations, and emphasized the need for planetary stewardship. Electrocatalytic processes enable the production of solar fuels and commodity chemicals that address universal issues of the water, energy and food security nexus, clothing, the building sector, heating and cooling, transportation, information and communication technology, chemicals, consumer goods and services, and healthcare, toward providing global resource security and sustainability and enhancing environmental and social justice.

Abolishing storage lipids induces protein misfolding and stress responses in Yarrowia lipolytica.

Yarrowia lipolytica naturally saves carbon excess as storage lipids. Engineering efforts allow redirecting the high precursor flux required for lipid synthesis towards added-value chemicals such as polyketides, flavonoids, and terpenoids. To redirect precursor flux from storage lipids to other products, four genes involved in triacylglycerol and sterol ester synthesis (DGA1, DGA2, LRO1, ARE1) can be deleted. To elucidate the effect of the deletions on cell physiology and regulation, we performed chemostat cultivations under carbon and nitrogen limitation, followed by transcriptome analysis. We found that storage lipid-free cells show an enrichment of the unfolded protein response, and several biological processes related to protein refolding and degradation are enriched. Additionally, storage lipid-free cells show an altered lipid class distribution with an abundance of potentially cytotoxic free fatty acids under nitrogen limitation. Our findings not only highlight the importance of lipid metabolism on cell physiology and proteostasis, but can also aid the development of improved chassy strains of Y. lipolytica for commodity chemical production.

Selective CO2 electrolysis to CO using isolated antimony alloyed copper

Renewable electricity-powered CO evolution from CO2 emissions is a promising first step in the sustainable production of commodity chemicals, but performing electrochemical CO2 reduction economically at scale is challenging since only noble metals, for example, gold and silver, have shown high performance for CO2-to-CO. Cu is a potential catalyst to achieve CO2 reduction to CO at the industrial scale, but the C-C coupling process on Cu significantly depletes CO* intermediates, thus limiting the CO evolution rate and producing many hydrocarbon and oxygenate mixtures. Herein, we tune the CO selectivity of Cu by alloying a second metal Sb into Cu, and report an antimony-copper single-atom alloy catalyst (Sb1Cu) of isolated Sb-Cu interfaces that catalyzes the efficient conversion of CO2-to-CO with a Faradaic efficiency over 95%. The partial current density reaches 452 mA cm−2 with approximately 91% CO Faradaic efficiency, and negligible C2+ products are observed. In situ spectroscopic measurements and theoretical simulations reason that the atomic Sb-Cu interface in Cu promotes CO2 adsorption/activation and weakens the binding strength of CO*, which ends up with enhanced CO selectivity and production rates.

EcBSU1: A Genome-Scale Enzyme-Constrained Model of Bacillus subtilis Based on the ECMpy Workflow.

Genome-scale metabolic models (GEMs) play an important role in the phenotype prediction of microorganisms, and their accuracy can be further improved by integrating other types of biological data such as enzyme concentrations and kinetic coefficients. Enzyme-constrained models (ecModels) have been constructed for several species and were successfully applied to increase the production of commodity chemicals. However, there was still no genome-scale ecModel for the important model organism Bacillus subtilis prior to this study. Here, we integrated enzyme kinetic and proteomic data to construct the first genome-scale ecModel of B. subtilis (ecBSU1) using the ECMpy workflow. We first used ecBSU1 to simulate overflow metabolism and explore the trade-off between biomass yield and enzyme usage efficiency. Next, we simulated the growth rate on eight previously published substrates and found that the simulation results of ecBSU1 were in good agreement with the literature. Finally, we identified target genes that enhance the yield of commodity chemicals using ecBSU1, most of which were consistent with the experimental data, and some of which may be potential novel targets for metabolic engineering. This work demonstrates that the integration of enzymatic constraints is an effective method to improve the performance of GEMs. The ecModel can predict overflow metabolism more precisely and can be used for the identification of target genes to guide the rational design of microbial cell factories.

Model-driven approach for the production of butyrate from CO2/H2 by a novel co-culture of C. autoethanogenum and C. beijerinckii.

One-carbon (C1) compounds are promising feedstocks for the sustainable production of commodity chemicals. CO2 is a particularly advantageous C1-feedstock since it is an unwanted industrial off-gas that can be converted into valuable products while reducing its atmospheric levels. Acetogens are microorganisms that can grow on CO2/H2 gas mixtures and syngas converting these substrates into ethanol and acetate. Co-cultivation of acetogens with other microbial species that can further process such products, can expand the variety of products to, for example, medium chain fatty acids (MCFA) and longer chain alcohols. Solventogens are microorganisms known to produce MCFA and alcohols via the acetone-butanol-ethanol (ABE) fermentation in which acetate is a key metabolite. Thus, co-cultivation of an acetogen and a solventogen in a consortium provides a potential platform to produce valuable chemicals from CO2. In this study, metabolic modeling was implemented to design a new co-culture of an acetogen and a solventogen to produce butyrate from CO2/H2 mixtures. The model-driven approach suggested the ability of the studied solventogenic species to grow on lactate/glycerol with acetate as co-substrate. This ability was confirmed experimentally by cultivation of Clostridium beijerinckii on these substrates in batch serum bottles and subsequently in pH-controlled bioreactors. Community modeling also suggested that a novel microbial consortium consisting of the acetogen Clostridium autoethanogenum, and the solventogen C. beijerinckii would be feasible and stable. On the basis of this prediction, a co-culture was experimentally established. C. autoethanogenum grew on CO2/H2 producing acetate and traces of ethanol. Acetate was in turn, consumed by C. beijerinckii together with lactate, producing butyrate. These results show that community modeling of metabolism is a valuable tool to guide the design of microbial consortia for the tailored production of chemicals from renewable resources.

Selfish uptake versus extracellular arabinoxylan degradation in the primary degrader Ruminiclostridium cellulolyticum, a new string to its bow

BackgroundPrimary degraders of polysaccharides play a key role in anaerobic biotopes, where plant cell wall accumulates, providing extracellular enzymes to release fermentable carbohydrates to fuel themselves and other non-degrader species. Ruminiclostridium cellulolyticum is a model primary degrader growing amongst others on arabinoxylan. It produces large multi-enzymatic complexes called cellulosomes, which efficiently deconstruct arabinoxylan into fermentable monosaccharides.ResultsComplete extracellular arabinoxylan degradation was long thought to be required to fuel the bacterium during this plant cell wall deconstruction stage. We discovered and characterized a second system of “arabinoxylan” degradation in R. cellulolyticum, which challenged this paradigm. This “selfish” system is composed of an ABC transporter dedicated to the import of large and possibly acetylated arabinoxylodextrins, and a set of four glycoside hydrolases and two esterases. These enzymes show complementary action modes on arabinoxylo-dextrins. Two α-L-arabinofuranosidases target the diverse arabinosyl side chains, and two exo-xylanases target the xylo-oligosaccharides backbone either at the reducing or the non-reducing end. Together, with the help of two different esterases removing acetyl decorations, they achieve the depolymerization of arabinoxylo-dextrins in arabinose, xylose and xylobiose. The in vivo study showed that this new system is strongly beneficial for the fitness of the bacterium when grown on arabinoxylan, leading to the conclusion that a part of arabinoxylan degradation is achieved in the cytosol, even if monosaccharides are efficiently provided by the cellulosomes in the extracellular space. These results shed new light on the strategies used by anaerobic primary degrader bacteria to metabolize highly decorated arabinoxylan in competitive environments.ConclusionThe primary degrader model Ruminiclostridium cellulolyticum has developed a “selfish” strategy consisting of importing into the bacterium, large arabinoxylan–dextrin fractions released from a partial extracellular deconstruction of arabinoxylan, thus complementing its efficient extracellular arabinoxylan degradation system. Genetic studies suggest that this system is important to support fitness and survival in a competitive biotope. These results provide a better understanding of arabinoxylan catabolism in the primary degrader, with biotechnological application for synthetic microbial community engineering for the production of commodity chemicals from lignocellulosic biomass.

Segregationally stabilised plasmids improve production of commodity chemicals in glucose-limited continuous fermentation

BackgroundThe production of chemicals via bio-based routes is held back by limited easy-to-use stabilisation systems. A wide range of plasmid stabilisation mechanisms can be found in the literature, however, how these mechanisms effect genetic stability and how host strains still revert to non-productive variants is poorly understood at the single-cell level. This phenomenon can generate difficulties in production-scale bioreactors as different populations of productive and non-productive cells can arise. To understand how to prevent non-productive strains from arising, it is vital to understand strain behaviour at a single-cell level.The persistence of genes located on plasmid vectors is dependent on numerous factors but can be broadly separated into structural stability and segregational stability. While structural stability refers to the capability of a cell to resist genetic mutations that bring about a loss of gene function in a production pathway, segregational stability refers to the capability of a cell to correctly distribute plasmids into daughter cells to maintain copy number. A lack of segregational stability can rapidly generate plasmid-free variants during replication, which compromises productivity.ResultsCitramalate synthase expression was linked in an operon to the expression of a fluorescent reporter to enable rapid screening of the retention of a model chemical synthesis pathway in a continuous fermentation of E. coli. Cells without additional plasmid stabilisation started to lose productivity immediately after entering the continuous phase. Inclusion of a multimer resolution site, cer, enabled a steady-state production period of 58 h before a drop in productivity was detected. Single-cell fluorescence measurements showed that plasmid-free variants arose rapidly without cer stabilisation and that this was likely due to unequal distribution of plasmid into daughter cells during cell division. The addition of cer increased total chemical yield by more than 50%.ConclusionsThis study shows the potential remains high for plasmids to be used as pathway vectors in industrial bio-based chemicals production, providing they are correctly stabilised. We demonstrate the need for accessible bacterial ‘toolkits’ to enable rapid production of known, stabilised bacterial production strains to enable continuous fermentation at scale for the chemicals industry.

Photoelectrochemical hydrogen evolution from biomass conversion using perovskite solar cells

Lignocellulosic biomass presents a renewable alternative to fossil carbon sources for the production of commodity chemicals and fuels. Photoelectrochemical biomass conversion produces carbon-free fuel in the form of molecular hydrogen and simultaneously provides a source of value-added chemical products. Recently in Nature Communication , S.Y. Jang, J.-W. Jang, J. Ryu, and co-workers reported bias-free photoelectrochemical solar hydrogen production coupled to lignocellulosic biomass degradation using a perovskite-based photocathode with anodic lignin depolymerization mediated by phosphomolybdic acid. Lignocellulosic biomass presents a renewable alternative to fossil carbon sources for the production of commodity chemicals and fuels. Photoelectrochemical biomass conversion produces carbon-free fuel in the form of molecular hydrogen and simultaneously provides a source of value-added chemical products. Recently in Nature Communication , S.Y. Jang, J.-W. Jang, J. Ryu, and co-workers reported bias-free photoelectrochemical solar hydrogen production coupled to lignocellulosic biomass degradation using a perovskite-based photocathode with anodic lignin depolymerization mediated by phosphomolybdic acid.

Reaction Pathways for the Electrochemical Synthesis of KA Oil from Cyclohexane

Recent decreases in the cost of electricity from both renewable and non-renewable sources and limitations of fossil fuel resources have bolstered interest in producing commodity chemicals using electrochemistry. Electrosynthesis offers promising alternatives to thermochemical processes, because they do not typically require extreme temperature and pressure. In addition, electric current can be used to replace dangerous reducing and oxidizing agents used in traditional organic chemistry. Electrosynthesis has been demonstrated as a possible pathway for partial oxidation of alkanes, which contain extremely inert C-H bonds.A major challenge in nylon 6,6 manufacturing is cyclohexane conversion to KA oil, a mixture of cyclohexanone and cyclohexanol. In the current industry, this process suffers from low cyclohexane conversion and pressure requirements. Although cyclohexane electrochemical oxidation to KA oil has been demonstrated in literature, the mechanism by which this occurs is still poorly understood.In this work, we demonstrate KA oil production through cyclohexane electrochemical oxidation in organic electrolytes. Using chronoamperometry, we identify the oxygen source (oxygen gas vs. water) for this reaction. In addition, we show that the cathodic counter reaction can influence cyclohexane conversion to KA oil and should be accounted for in mechanistic experiments. Based on literature, side product analysis, and electroanalytical methods, we propose a reaction pathway for electrochemical cyclohexane conversion to KA oil.

An annotated selection of World Wide Web sites relevant to the topics in microbial biotechnology.

This U.S. Department of Energy site focuses on the use of microbial fuel cells to convert biomass to hydrogen as a source of chemical energy. This is a review article on converting biomass using microbial fuel cells. This page describes a process whereby cellulose is broken down by fungi and the sugars converted to lactic acid. Lactic acid, in turn, serves as the microbial feedstock for the production of other commodity chemicals. A critical issue in biorefining is to determine the best targets chemicals to make microbiologically. One criteria examined is the savings in greenhouse gas emissions by making a given chemical biologically in comparison with a fossil-fuel derivation. This site provides a comprehensive resource regarding biorefineries: How many exist, the types, which feedstocks they use, and what products are generated. BioMADE is a relatively new centre with a mission to promote U.S. bioindustrial manufacturing at a competitive scale. Most projects are based on microbial biotechnology research which is then scaled for practical use. This broad-based review article examines the biomass composition of earth with respect to taxonomy, geographic location and trophic levels. The ability to use lignin as a source of carbon in manufacturing would be highly significant. The present study used Pseudomonas putida as a platform for synthetic biology, building on natural abilities to metabolize lignin aromatics. This review article comprehensively examines developments in the microbiological conversion of lignin, which it describes as ‘the world's most underutilized renewable’. It is considered here that both microbiological and hybrid biological/catalytic processes for lignocellulose conversion may ultimately prove to be economical. Cellulase reacts processively along a cellulose polymer and also acts as part of a multi-enzyme complex to efficiently deconstruct the biopolymer.

Steering Catalytic Selectivity with Atomically Dispersed Metal Electrocatalysts for Renewable Energy Conversion and Commodity Chemical Production.

Electrocatalysis is a key driver in promoting the paradigm shift from the current fossil-fuel-based hydrocarbon economy to a renewable-energy-driven hydrogen economy. The success of electrocatalysis hinges primarily on achieving high catalytic selectivity along with maximum activity and sustained longevity. Many electrochemical reactions proceed through multiple pathways, requiring highly selective catalysts.Atomically dispersed metal catalysts have emerged as a new frontier in heterogeneous catalysis. In addition to the widely perceived advantages of maximized active site utilization and substantially reduced metal content, they have shown different catalytic selectivities in some electrocatalytic reactions compared to the traditional nanoparticle (NP)-based catalysts. Although there have been significant advances in their synthesis, the highly energetic nature of a single atomic site has made the preparation of atomically dispersed metal catalysts rely on empiricism rather than rational design. Consequently, the structural comprehension of a single atomic site and the understanding of its unusual electrocatalytic selectivity remain largely elusive.In this Account, we describe our endeavors toward developing general synthetic approaches for atomically dispersed metal catalysts for the discovery of new selective and active electrocatalysts and to understand their catalytic nature. We introduce synthetic approaches to produce a wide range of nonprecious- and precious-metal-based atomically dispersed catalysts and control their coordination environments. Metallomacrocyclic-compound-driven top-down and metal salt/heteroatom layer-based bottom-up strategies, coupled with a SiO2-protective-layer-assisted method, have been developed that can effectively generate single atomic sites while mitigating the formation of metallic NPs. The low-temperature gas-phase ligand exchange method can reversibly tune the coordination structure of the atomically dispersed metal sites. We have used the prepared atomically dispersed metal catalysts as model systems to investigate their electrocatalytic reactivity for renewable energy conversion and commodity chemical production reactions, in which high selectivity is important. The reactions of our interest include the following: (i) the oxygen reduction reaction, where O2 is reduced to either H2O or H2O2 via the four-electron or two electron pathway, respectively; (ii) the CO2 reduction reaction, which should suppress the hydrogen evolution reaction; and (iii) the chlorine evolution reaction, which competes with the oxygen evolution reaction. The type of metal center to which the reactant is directly bound is found to be the most important in determining the selectivity, which originates from the dramatic changes in the binding energy of each metal center with the reactants. The coordination structure surrounding the metal center also has a significant effect on the selectivity; its control can modulate the oxidation state of the metal center, thereby altering the binding strength with the reactants.We envisage that future advances in the synthesis of atomically dispersed metal catalysts, combined with the growing power of computational, spectroscopic, and microscopic methods, will bring their synthesis to the level of rational design. Elaborately designed catalysts can overcome the current limits of catalytic selectivity, which will help establish the field of atomically dispersed metal catalysts as an important branch of catalysis.

Non‐siliceous ordered mesoporous materials via nanocasting for small molecule conversion electrocatalysis

AbstractSince the pioneering work of Ryoo and co‐workers in 1999 on the synthesis of ordered mesoporous carbons via nanocasting, the nanocasting pathway has endured the test of time and has established itself as a robust and versatile method for preparing ordered mesoporous materials (OMMs). This method enables the generation of a remarkably wide range of non‐siliceous OMMs, some of which are otherwise inaccessible. In this account, we present our decade‐long efforts toward the function‐oriented design of non‐siliceous OMM‐based electrocatalysts for promoting small molecule conversion reactions relevant to renewable energy conversion and commodity chemical production, including hydrogen evolution reaction, oxygen evolution reaction, and selective oxygen reduction reaction. We also discuss the extension of the nanocasting concept to a silica‐coating‐mediated synthesis for preparing new catalytic materials. We conclude the account by suggesting the remaining challenges and outlook for the future development of advanced OMMs.

Bubbles pinned on electrodes: Friends or foes of aqueous electrochemistry?

Electrochemists and engineers regard adherent gas bubbles as redox-inactive and therefore blocking entities. Adhesion of bubbles at electrodes generally carries an energy penalty. But this is not always the case: bubbles pinned on an electrode surface initiate the oxidation of water-soluble species under conditions where such reactions would normally be considered impossible. Here we critically review the recent literature that is beginning to unveil the novel concept of on-water electrochemistry. Harnessing electrochemical reactivity of the water–gas–electrode interface has the potential to become a game-changer in organic electrosynthesis, accelerating the transition toward a sustainable chemical industry by simplifying the direct integration of renewable electricity into the production of commodity chemicals.

(Invited) Process Intensification of Electrochemical Systems for CO2 and Biomass Valorization

Valorization of CO2 and biomass waste streams via electrochemical conversions is a sustainable alternative for the production of fine chemicals and commodity chemicals. This topic has gained a lot of attention in the past decades and major research efforts have been put into it. Key advances has been achieved in the field of material development, where, novel catalysts have been synthesized, developed and have demonstrated to increase the efficiency and selectivity towards the targeted products. Relatively to the large number of studies focused on material development, limited studies are focused on process development, reactor optimization and product separation. Although material development is of paramount importance to achieve an adequate electrochemical reaction performance, it is only the first step needed in order to develop a competitive technology. Process development offers the possibility of enhancing the overall performance of the technology by looking not only at the reaction level, but finding engineering solutions to overcome critical limitations. Process development is essential in order to accelerate the technology towards its envisioned application and advance towards commercial realization. In this talk, we will present several optimization strategies (beyond material development) that helped increase the overall performance of several electrochemical conversion processes, as well as the economic profitability of the complete system.In addition, in order to advance the technology on the TRL scale and have a positive market potential, the technology needs to be evaluated in several aspects such as the scaling-up challenges, its cost competitiveness and its climate benefits. For this, it is crucial to consider the complete value chain, and evaluate not only the electrochemical reaction but also the upstream and the downstream processes. A complete system approach is paramount for the development of competitive technologies. In this talk we will also show several examples on different process intensification strategies and its benefits on the economic potential of them.