Two Decades of Laccases: Advancing Sustainability in the Chemical Industry

Given the current state of environmental affairs and that our future on this planet as we know it is in jeopardy, research and development into greener and more sustainable technologies within the chemical and forest products industries is at its peak. Given the global scale of these industries, the need for environmentally benign practices is propelling new green processes. These challenges are also impacting academic research and our reagents of interest are laccases. These enzymes are employed in a variety of biotechnological applications due to their native function as catalytic oxidants. They are about as green as it gets when it comes to chemical processes, requiring O₂ as their only co‐substrate and producing H₂O as the sole by‐product. The following account will review our twenty year journey on the use of these enzymes within our research group, from their initial use in biobleaching of kraft pulps and for fiber modification within the pulp and paper industry, to their current application as green catalytic oxidants in the field of synthetic organic chemistry.     

Review on electrochemical carbon dioxide capture and transformation with bipolar membranes

Anthropogenic carbon dioxide(CO₂ ) emission from the combustion of fossil fuels aggravates the global greenhouse effect. The implementation of CO₂ capture and transformation technologies have recently received great attention for providing a pathway in dealing with global climate change. Among these technologies, electrochemical CO₂ capture technology has attracted wide attention because of its environmental friendliness and flexible operating processes. Bipolar ...     

CO2 – Baustein des Lebens und Treiber der globalen Erwärmung

For hundreds of millions of years, nature uses carbon dioxide in photosynthesis as a vital building block of life. The compound is also an essential part of the carbon cycle and is co‐responsible for the transport of carbon between Earth's spheres. However, over the last years CO₂ has been closely associated with global warming since the immense emissions from mainly the burning of fossil resources has led to a vast increase in atmospheric CO₂‐levels. Therefore, not only a reduction of emissions on a global scale is crucial but also a trend towards renewable resources is clearly visible and necessary due to depleting fossil resources. In this context, the use of CO₂ as an abundant resource in the chemical industry can contribute its share.     

Synthesis of Acetoaldehyde,Acetic Acid,and Others by the Dehydrogenation and Oxidation of Ethanol

Following gradual shift of primary resources from fossil towards renewable ones in chemical industry, biomass based ethanol has been attracting growing interests as a fuel to replace gasoline and as a chemical feed stock to replace ethylene. This paper reviews major work reported in the last 10 years for the production of acetaldehyde, acetic acid, and other related compounds from ethanol. At present acetic acid can be industrially produced more economically from methanol than from ethylene, the production of acetic acid from ethanol is not profitable. Acetaldehyde, which is more expensive than ethanol, can be selectively produced in gas phase by dehydrogenation over supported Cu catalysts and by oxidation with O₂ over V and Mo based oxides. It is noteworthy that gold nanoparticles deposited on basic and acidic metal oxides are highly selective to acetaldehyde by oxidation with O₂. Acetic acid can be produced in water solvent over Au catalysts supported on MgAl₂O₄ or on Cu doped NiO, while in gas phase over Mo–V–Nb mixed oxides combined with TiO₂ colloids.     

Metabolic engineering is key to a sustainable chemical industry

The depletion of fossil fuel stocks will prohibit their use as the main feedstock of future industrial processes. Biocatalysis is being increasingly used to reduce fossil fuel reliance and to improve the sustainability, efficiency and cost of chemical production. Even with their current small market share, biocatalyzed processes already generate approximately US$50 billion and it has been estimated that they could be used to produce up to 20% of fine chemicals by 2020. Until the advent of molecular biological technologies, the compounds that were readily accessible from renewable biomass were restricted to naturally-occurring metabolites. However, metabolic engineering has considerably broadened the range of compounds now accessible, providing access to compounds that cannot be otherwise reliably sourced, as well as replacing established chemical processes. This review presents the case for continued efforts to promote the adoption of biocatalyzed processes, highlighting successful examples of industrial chemical production from biomass and/or via biocatalyzed processes. A selection of emerging technologies that may further extend the potential and sustainability of biocatalysis are also presented. As the field matures, metabolic engineering will be increasingly crucial in maintaining our quality of life into a future where our current resources and feedstocks cannot be relied upon.     

Pervaporation-based hybrid process: a review of process design,applications and economics

Pervaporation is one of the developing membrane technologies that can be used for various industrial applications but for a predefined task, the optimal process design is unlikely to consist solely of pervaporation. Often the optimised solution becomes a hybrid process combining pervaporation with one or more other separation technologies. A distinction will be made between hybrid and integrated processes. Hybrid processes are important and consequently need to be considered in process design. This paper focuses on pervaporation–based hybrid processes that have been realised on an industrial scale. Both present and future prospects of applying these process combinations will be reviewed. The emphasis of this paper is, therefore, on pervaporation combined with distillation and with chemical reactors. The economic potential of these hybrid processes is evaluated, for various applications, by cost comparisons between the pervaporation-based hybrid processes and alternative separation processes. Pervaporation-based processes for waste water treatment and biotechnology applications involve other types of pervaporation based hybrid processes and have been excluded from this review.     

Treatment and Disposal of Pharmaceutical Wastewater: Toward the Sustainable Strategy

The literature on the treatment of pharmaceutical wastewater over the period 1990–2015 has been reviewed to develop a sustainable treatment strategy. Analysis of the existing methods for treatment and disposal practices of pharmaceutical waste has been undertaken on the classification of the treatment methods under well-identified broad specific groups. The review reveals the associated merits and demerits of the traditional and the emerging methods and the challenges involved in overcoming the shortcomings. Considering the very diverse nature of the contaminants and the poor success rates of the existing technologies, it transpires that no single classical technology is capable of fully taking care of the hazards emanating from pharmaceutical waste discharges. On the other hand, some recent technologies such as membrane-integrated hybrid technologies are emerging as more successful ones than the conventional technologies. But, scale up confidence with respect to such new technologies is still very limited and needs to be substantially improved through extensive investigation on the pilot scale using real pharmaceutical wastewater rather than synthetic wastewater. This review directs the research focus to the development of sustainable treatment technologies.     

The Legacy of Fossil Fuels

Currently, over 80 % of the energy used by mankind comes from fossil fuels. Harnessing coal, oil and gas, the energy resources contained in the store of our spaceship, Earth, has prompted a dramatic expansion in energy use and a substantial improvement in the quality of life of billions of individuals in some regions of the world. Powering our civilization with fossil fuels has been very convenient, but now we know that it entails severe consequences. We treat fossil fuels as a resource that anyone anywhere can extract and use in any fashion, and Earth’s atmosphere, soil and oceans as a dump for their waste products, including more than 30 Gt/y of carbon dioxide. At present, environmental legacy rather than consistence of exploitable reserves, is the most dramatic problem posed by the relentless increase of fossil fuel global demand. Harmful effects on the environment and human health, usually not incorporated into the pricing of fossil fuels, include immediate and short‐term impacts related to their discovery, extraction, transportation, distribution, and burning as well as climate change that are spread over time to future generations or over space to the entire planet. In this essay, several aspects of the fossil fuel legacy are discussed, such as alteration of the carbon cycle, carbon dioxide rise and its measurement, greenhouse effect, anthropogenic climate change, air pollution and human health, geoengineering proposals, land and water degradation, economic problems, indirect effects on the society, and the urgent need of regulatory efforts and related actions to promote a gradual transition out of the fossil fuel era. While manufacturing sustainable solar fuels appears to be a longer‐time perspective, alternatives energy sources already exist that have the potential to replace fossil fuels as feedstocks for electricity production.     

Supported CuII Single-Ion Catalyst for Total Carbon Utilization of C2 and C3 Biomass-Based Platform Molecules in the N-Formylation of Amines

The shift from fossil carbon sources to renewable ones is vital for developing sustainable chemical processes to produce valuable chemicals. In this work, value-added formamides were synthesized in good yields by the reaction of amines with C₂ and C₃ biomass-based platform molecules such as glycolic acid, 1,3-dihydroxyacetone and glyceraldehyde. These feedstocks were selectively converted by catalysts based on Cu-containing zeolite 5A through the in situ formation of carbonyl-containing intermediates. To the best of our knowledge, this is the first example in which all the carbon atoms in biomass-based feedstocks could be amidated to produce formamide. Combined catalyst characterization results revealed preferably single Cu^II sites on the surface of Cu/5A, some of which form small clusters, but without direct linking via oxygen bridges. By combining the results of electron paramagnetic resonance (EPR) spin-trapping, operando attenuated total reflection (ATR) IR spectroscopy and control experiments, it was found that the formation of formamides might involve a HCOOH-like intermediate and ^.NHPh radicals, in which the selective formation of ^.OOH radicals might play a key role.     

Chemical imaging of catalytic solids with synchrotron radiation

Heterogeneous catalysis is a term normally used to describe a group of catalytic processes, yet it could equally be employed to describe the catalytic solid itself. A better understanding of the chemical and structural variation within such materials is thus a pre-requisite for the rationalising of structure-function relationships and ultimately to the design of new, more sustainable catalytic processes. The past 20 years has witnessed marked improvements in technologies required for analytical measurements at synchrotron sources, including higher photon brightness, nano-focusing, rapid, high resolution data acquisition and in the handling of large volumes of data. It is now possible to image materials using the entire synchrotron radiative profile, thus heralding a new era of in situ/operando measurements of catalytic solids. In this tutorial review we discuss the recent work in this exciting new research area and finally conclude with a future outlook on what will be possible/challenging to measure in the not-too-distant future.     

Transformations of biomass-derived platform molecules: from high added-value chemicals to fuels via aqueous-phase processing

Global warming issues and the medium-term depletion of fossil fuel reserves are stimulating researchers around the world to find alternative sources of energy and organic carbon. Biomass is considered by experts the only sustainable source of energy and organic carbon for our industrial society, and it has the potential to displace petroleum in the production of chemicals and liquid transportation fuels. However, the transition from a petroleum-based economy to one based on biomass requires new strategies since the petrochemical technologies, well-developed over the last century, are not valid to process the biomass-derived compounds. Unlike petroleum feedstocks, biomass derived platform molecules possess a high oxygen content that gives them low volatility, high solubility in water, high reactivity and low thermal stability, properties that favour the processing of these resources by catalytic aqueous-phase technologies at moderate temperatures. This tutorial review is aimed at providing a general overview of processes, technologies and challenges that lie ahead for a range of different aqueous-phase transformations of some of the key biomass-derived platform molecules into liquid fuels for the transportation sector and related high added value chemicals.     

10 years after rio-concepts on the contribution of chemistry to a sustainable development

The principles of the United Nations Conference on Environment and Development (UNCED), held in June 1992 in Rio de Janeiro, and Agenda 21, the comprehensive plan of action for the 21st century, adopted 10 years ago by more than 170 governments, address the pressing problems of today and also aim at preparing the world for the challenges of this century. The conservation and management of resources for development are the main focus of interest, to which the sciences will have to make a considerable contribution. Natural, economic, and social sciences will have to be integrated in order to achieve this aim. In their future programs, the associations of the chemical industries in Europe, Japan, and the USA have explicitly accepted their obligation to foster a sustainable development.In this review we investigate innovations in chemistry exemplarily for such a development with regard to their ecological, economical, and social dimensions from an integrated and interdisciplinary perspective. Since base chemicals are produced in large quantities and important product lines are synthesized from them, their resource-saving production is especially important for a sustainable development. This concept has been shown, amongst others, by the example of the syntheses of propylene oxide and adipic acid. In the long run, renewable resources that are catalytically processed could replace fossil raw materials. Separation methods existing today must be improved considerably to lower material and energy consumption. Chemistry might become the pioneer of an innovative energy technique.The design of chemical products should make possible a sustainable processing and recycling and should prevent their bio-accumulation. Methods and criteria to assess their contribution to a sustainable development are necessary. The time taken to introduce the new more sustainable processes and products has to be diminished by linking their development with operational innovation management and with efficient environmental-political control procedures.     

Non-thermal plasma technology for the conversion of CO2

The conversion of carbon dioxide is vital if we are to avoid the catastrophic consequences that will result from further global temperature rise as a result of burning fossil fuels. Current techniques, such as catalytic conversion and biochemical processes, are each associated with their own drawbacks such as catalyst deactivation and high energy input. Plasma processes are gaining increasing interest as they have the potential to reduce a greater amount of atmospheric environmental pollutants at any one time due to an increased throughput, whilst using a smaller reactor with improved energy efficiency and near-zero emissions. Non-thermal plasma can dissociate stable molecules, such as CO₂, at temperatures as low as room temperature. It is this key feature which makes plasma conversion such a promising technology in the conversion and utilisation of CO₂. Furthermore, possible products from plasma processes include fuels and chemicals, such as methanol and syngas, which have a high market value; hence potentially making the process feasible on an industrial scale. This paper discusses recent advances in the use of plasma processes for carbon dioxide conversion, along with the future outlook of this technology and the impact these techniques could have on the chemical and energy industries.     

Selective Catalytic Synthesis Using the Combination of Carbon Dioxide and Hydrogen: Catalytic Chess at the Interface of Energy and Chemistry

The present Review highlights the challenges and opportunities when using the combination CO₂/H₂ as a C₁ synthon in catalytic reactions and processes. The transformations are classified according to the reduction level and the bond‐forming processes, covering the value chain from high volume basic chemicals to complex molecules, including biologically active substances. Whereas some of these concepts can facilitate the transition of the energy system by harvesting renewable energy into chemical products, others provide options to reduce the environmental impact of chemical production already in today's petrochemical‐based industry. Interdisciplinary fundamental research from chemists and chemical engineers can make important contributions to sustainable development at the interface of the energetic and chemical value chain. The present Review invites the reader to enjoy this exciting area of “catalytic chess” and maybe even to start playing some games in her or his laboratory.     

Electrochemical Cross-Dehydrogenative Coupling between Phenols and β-Dicarbonyl Compounds: Facile Construction of Benzofurans

Preparative electrochemical synthesis is an ideal method for establishing green, sustainable processes. The major benefits of an electro-organic strategy over that of conventional chemical synthesis are the avoidance of reagent waste and mild reaction conditions. Here, an intermolecular cross-dehydrogenative coupling between phenols and β-dicarbonyl compounds has been developed to build various benzofurans under undivided electrolytic conditions. Neither transition metals nor external chemical oxidants are required to facilitate the dehydrogenation and dehydration processes. The key factor in success was the use of nBu₄NBF₄ as the electrolyte and hexafluoroisopropanol as the solvent, which play key roles in the cyclocondensation step. This electrolysis is scalable and can be used as a key step in drug synthesis. On the basis of several experimental results, the mechanism, particularly of the remarkable anodic oxidation and cyclization process, was illustrated.     

Manganese-Catalyzed Sustainable Synthesis of Pyrroles from Alcohols and Amino Alcohols

The development of reactions that convert alcohols into important chemical compounds saves our fossil carbon resources as alcohols can be obtained from indigestible biomass such as lignocellulose. The conservation of our rare noble metals is of similar importance, and their replacement by abundantly available transition metals, such as Mn, Fe, or Co (base or nonprecious metals), in key technologies such as catalysis is a promising option. Herein, we report on the first base-metal-catalyzed synthesis of pyrroles from alcohols and amino alcohols. The most efficient catalysts are Mn complexes stabilized by PN₅P ligands whereas related Fe and Co complexes are inactive. The reaction proceeds under mild conditions at catalyst loadings as low as 0.5 mol %, and has a broad scope and attractive functional-group tolerance. These findings may inspire others to use Mn catalysts to replace Ir or Ru complexes in challenging dehydrogenation reactions.     

Glycerol and Glycerol-Based Deep Eutectic Mixtures as Emerging Green Solvents for Polyphenol Extraction: The Evidence So Far

The acknowledgement that uncontrolled and excessive use of fossil resources has become a prime concern with regard to environmental deterioration, has shifted the orientation of economies towards the implementation of sustainable routes of production, through the valorization of biomass. Green chemistry plays a key role in this regard, defining the framework of processes that encompass eco-friendly methodologies, which aim at the development of highly efficient production of numerous bioderived chemicals, with minimum environmental aggravation. One of the major concerns of the chemical industry in establishing sustainable routes of production, is the replacement of fossil-derived, volatile solvents, with bio-based benign ones, with low vapor pressure, recyclability, low or no toxicity, availability and low cost. Glycerol is a natural substance, inexpensive and non-toxic, and it is a principal by-product of biodiesel industry resulting from the transesterification process. The ever-growing market of biodiesel has created a significant surplus of glycerol production, resulting in a concomitant drop of its price. Thus, glycerol has become a highly available, low-cost liquid, and over the past decade its use as an alternative solvent has been gaining unprecedented attention. This review summarizes the utilization of glycerol and glycerol-based deep eutectic mixtures as emerging solvents with outstanding prospect in bioactive polyphenol extraction.     

Toward developing accelerated stress tests for proton exchange membrane electrolyzers

Proton exchange membrane water electrolysis is technically the most suitable technology for the production of green hydrogen on a large scale. Although it is still more expensive than hydrogen produced from fossil sources, it has already been commercialized. Novel components with cost-effective materials and efficient manufacturing processes are being rapidly developed. However, these components must endure durability tests that can guarantee a lifetime of at least 50,000 operation hours. Consequently, there is an urgent need to develop accelerated stress test protocols based on a deep understanding of degradation mechanisms of stack components. Recent reports show that the main degradation mechanisms are associated to anode catalyst dissolution, membrane chemical decomposition, and formation of semiconducting oxides on the metal components. These mechanisms can be accelerated by stressors such as high current density, dynamic operation, and shutdown modes. On the basis of these reports and knowledge of the operational requirements for large-scale proton exchange membrane water electrolysis, we propose an accelerated stress test protocol for the fast evaluation of newly developed cost efficient and durable components.     

Inevitable revival of C1 chemistry in the first half of the twenty-first century

The future of fuel production via C₁ chemistry is discussed in this paper. Four different processes from coal or natural gas to methanol or gasoline are compared with the present commercialized process from crude oil to gasoline on the aspects of economics, environmental friendliness and energy. Considering the future trend of crude oil price, it is believed that C₁ chemical technologies, especially indirect conversion technologies, will become economically feasible by the year 2030.