Research Shoubhik Das

Abstract

C-H bond oxygenation reactions are highly important as they increase the accessibility of pharmaceuticals in a sustainable way. So far, mainly homogeneous catalysts exist for these reactions and most of these strategies suffer from limited scope, the use of high loading of expensive and complex catalysts, use of expensive oxidants, and low recyclability or selectivity. Replacing the strong oxidants by oxygen and introducing heterogeneous photocatalysts can bring selectivity in these reactions and will surely enhance sustainability. While homogeneous photocatalysts render high atom efficiencies and selectivity, heterogeneous catalysts are more preferable on an industrial level due to their recyclability, robustness and economic nature. To achieve this target, I will develop novel and robust heterogeneous photocatalysts which will provide high selectivity and should be recyclable after the oxygenation reactions. At the end, detailed characterizations and mechanistic experiments will allow us to design wide applications of this strategy.

Researcher(s)

• Promoter: Das Shoubhik
• Promoter: Maes Bert
• Co-promoter: Das Shoubhik
• Fellow: Vanderghinste Jaro

Research team(s)

• Organic synthesis (ORSY)

Project type(s)

• Research Project

Abstract

Utilization of carbon-rich fossil fuels and chemical feedstocks, including coal, oil and natural gas, has led to tremendous prosperity. However, the focus on wealth creation largely ignored the parallel adverse side effects, such as the increased level of CO2 in the atmosphere which results in climate change. There has been significant progress converting CO2 into fuels using catalytic and electrochemical processes. However, less efforts have been devoted to the discovery of new heterogeneous catalysts that use CO2 as a synthon for the synthesis of fine chemicals and pharmaceuticals. This proposal is concerned with the development of heterogeneous catalysts for the dicarbofunctionalization of alkynes and alkenes to afford carboxylic acids and related derivatives using CO2 as the carbon source. These catalysts will be used to synthesize derivatives of a range of organic motifs including functionally challenging molecules present in the pharmaceuticals. At the end of the project, a toolbox of catalysts is anticipated that provide economically attractive routes to use CO2 for the synthesis of medicines and potentially other products.

Researcher(s)

• Promoter: Das Shoubhik
• Promoter: Maes Bert
• Co-promoter: Das Shoubhik
• Fellow: Cauwenbergh Robin

Research team(s)

• Organic synthesis (ORSY)

Project type(s)

• Research Project

Abstract

The synthesis of optically pure compounds is becoming increasingly important, as the global market for chiral chemicals is estimated to reach USD 120 billion by 2024 at a CAGR of 13.67%. Within the group of these chiral molecules, carboxylic acids and derivatives are especially indispensable for the pharmaceutical industry. This project proposal attempts to establish a synthesis for carboxylic acids and derivatives via functionalization of the stable C(sp3)-H bond by using CO2 as sustainable C1 synthon in the presence of cooperative photoredox catalysis. The mild reaction conditions, in combination with a catalytic system using naturally abundant metals, should make this innovative reactivity concept applicable for the direct C-H functionalization of a range of different C-H bonds in simple molecules, as well as C-H bonds in more 'functionally challenging' compounds such as those found in natural products or complex pharmaceutical agents.

Researcher(s)

• Promoter: Das Shoubhik
• Co-promoter: Maes Bert

Research team(s)

• Organic synthesis (ORSY)

Project type(s)

• Research Project

Abstract

The chemical industry in Flanders is of major importance at several levels. It provides 10% of all employment in Flanders, is home of the largest petrochemical cluster in Europe and is the main location of 10 out of the world's top 20 chemical companies. The chemical industry stands for more or less 50% of all R&D expenditures in Flanders and for 30% of all industrial investments in Belgium. Flanders is located at the heart of the Antwerp-Rotterdam-Rhine-Ruhr area, Europe's strongest industrial mega-cluster with 80% for Europe's purchasing power located within a radius of 800 km (Flanders Investment & Trade). Recently, some major investments have been made. In 2017, Kaneka strengthened its future in the region by announcing an investment of EUR 34 million in a third modified silicone (MS) polymer production line at its facility in Westerlo. Borealis is investing 1 billion Euro into the construction of a new propylene factory in Antwerp. The British chemical concern INEOS will be funneling 3 billion Euro into the expansion of its local chemical plant, which represents the largest chemical investment in Europe of the past two decades. The pinnacle of the investment is an ethane gas cracker, one of the largest in the world. No need to say that chemical research is a key area in Flanders, and that sustainability in the chemical sector is crucial for a very densely populated region. Furthermore, it will be essential to continue to innovate our chemical production in order to remain competitive compared to emerging (and already existing) industrial powers such as China, India, Brazil and Indonesia. Indeed, Asia's chemical production has already surpassed that of the rest of the world. Contributing to this, China is by far the biggest chemical producer in sales. On top of that, the growth in the global economy has slowed down in recent years. Generally speaking, business investment is weak, cross-border trade in goods and services is dwindling, and physical goods are under persistent deflationary pressures. Therefore, the outlook for growth in Europe remains unpromising, as demand continues to be weak. In this context, Flanders need to be aware of the changing world and invest in research and innovation. The European Commission is now developing the Horizon Europe program in order to stimulate the necessary internal changes to create "a smart, sustainable and inclusive economy". The development of new technologies to produce chemicals in a sustainable way will be a key issue to keep the European chemical industry in a strong position. If Flanders wants to maintain an important role in the European chemical industry, it will have to develop competitive tools to enable a more efficient and sustainable production.

Researcher(s)

• Promoter: Das Shoubhik

Research team(s)

• Organic synthesis (ORSY)

Project type(s)

• Research Project

Abstract

Renewable energy driven chemistry is necessary for the development of a sustainable economy. As a result, CO2 should not be regarded as a waste rather should be considered as a chemical feedstock. Converting this CO2 into useful fine chemicals and pharmaceuticals will provide access to high-value products from a non-toxic, renewable, and low-cost resource. In fact, visible-light-mediated transformation of CO2 to fine chemicals have already been achieved to promote this concept. However, current methods use expensive and toxic reagents along with expensive transition metal catalysts. In contrast, metal-free catalysts and systems are cheaper in price, use less carbon footprint, and are an interesting avenue to explore. Based on this concept, we would like to achieve carboxylic acids and their derivatives (lactams, lactones) via functionalization of non-activated C-H bonds. It is our strong opinion that in this way CO2-based chemistry can be changed and this should have tremendous impact in economic issues.

Researcher(s)

• Promoter: Das Shoubhik

Research team(s)

• Organic synthesis (ORSY)

Project type(s)

• Research Project

Abstract

This IOF consortium connects chemists, engineers, economic and environmental oriented researchers in an integrated team to maximize impact in key enabling sustainable chemical technologies, materials and reactors that are able to play a crucial role in a sustainable chemistry and economic transition to a circular, resource efficient and carbon neutral economy (part of the 2030 and 2050 goals in which Europe aims to lead). Innovative materials, renewable chemical feedstocks, new/alternative reactors, technologies and production methods are essential and central elements to achieve this goal. Due to their mutual interplay, a multidisciplinary, concerted effort is crucial to be successful. Furthermore, early on prediction and identification of strengths, opportunities, weaknesses and threats in life cycles, techno-economics and sustainability are key to allow sustainability by design and create effective knowledge-based decision-making and focus. The consortium focuses on sustainable chemical production through efficient and alternative energy use connected to circularity, new chemical pathways, technologies, reactors and materials, that allow the use of alternative feedstock and energy supply. These core technical aspects are supported by expertise in simulation, techno-economic and environmental impact assessment and uncertainty identification to accelerate technological development via knowledge-based design and early stage identified key research, needed for accelerated growth and maximum impact on sustainability. To achieve these goals, the consortium members are grouped in 4 interconnected valorisation programs focusing on key performance elements that thrive the chemical industry and technology: 1) renewable building blocks; 2) sustainable materials and materials for sustainable processes; 3) sustainable processes, efficiently using alternative renewable energy sources and/or circular chemical building blocks; 4) innovative reactors for sustainable processes. In addition, cross-cutting integrated enablers are present, providing expertise and essential support to the 4 valorisation programs through simulation, techno-economic and environmental impact assessment and uncertainty analysis.

Researcher(s)

• Promoter: Meynen Vera
• Co-promoter: Billen Pieter
• Co-promoter: Bogaerts Annemie
• Co-promoter: Breugelmans Tom
• Co-promoter: Compernolle Tine
• Co-promoter: Cool Pegie
• Co-promoter: Das Shoubhik
• Co-promoter: Lenaerts Silvia
• Co-promoter: Maes Bert
• Co-promoter: Neyts Erik
• Co-promoter: Perreault Patrice
• Co-promoter: Vande Velde Christophe
• Co-promoter: Vande Velde Christophe
• Co-promoter: Van Passel Steven
• Co-promoter: Verbruggen Sammy
• Fellow: Meyer Nathalie

Research team(s)

• Laboratory of adsorption and catalysis (LADCA)

Project type(s)

• Research Project

Abstract

This is a fundamental research project financed by the Research Foundation – Flanders (FWO). The project was subsidized after selection by the FWO-expert panel. The objective of the FWO's Research projects is to advance fundamental scientific research.

Researcher(s)

• Promoter: Maes Bert
• Co-promoter: Das Shoubhik

Research team(s)

• Organic synthesis (ORSY)

Project type(s)

• Research Project

Abstract

This application relates to replacement of an old Agilent 7890A/5975C GC-FID-MS instrument. This instrument was installed in 2009 and is currently outdated. As a replacement, we intend to purchase the state of the art Agilent 8890 instrument equipped with an Agilent 5977B single quadrupole MS Detector.

Researcher(s)

• Promoter: Das Shoubhik
• Co-promoter: Maes Bert

Research team(s)

• Organic synthesis (ORSY)

Project type(s)

• Research Project

Abstract

Hydrogen peroxide (H2O2) is a versatile, environmentally friendly oxidizing agent and considered as one of the 100 most important chemicals in the world. Among the many chemical oxidants available to the chemists, H2O2 is considered as one of the ''greenest'' since the by-product of its oxidation is only water. Additionally, it is also one of the most efficient oxidizing agents by virtue of its high active oxygen content (about 47%), only next to molecular oxygen. The current global market size for hydrogen peroxide (H2O2) has reached to 4 billion USD with a compound annual growth rate of more than 5% from 2020 to 2024. Currently, H2O2 is produced via the anthraquinone oxidation (AO) process and has been successfully used to produce most of the world's H2O2. However, the AO process suffers from several drawbacks, such as use of complex and toxic solvent system, periodic replacement of costly quinone-derivative due to nonselective hydrogenation, deactivation of hydrogenation catalyst, requirements of energy intensive process steps for the removal of organic impurities, etc. Based on these, we have developed an operationally simple and green approach for the synthesis of H2O2 directly from renewable resources using photocatalysis.

Researcher(s)

• Promoter: Das Shoubhik

Research team(s)

• Organic synthesis (ORSY)

Project website

Project type(s)

• Research Project

Abstract

Formic acid (FA) is well-known as a promising hydrogen source as well as a valuable chemical for the industries of textiles, pharmaceuticals etc. In fact, 1.137 million metric tons of FA is required per year over the entire world to meet the current demand. Therefore, there is a strong interest for the generation of FA in a sustainable way to meet the future demand. Inspired by this information, we propose a solar energy mediated method to generate FA from the biomass. This method involves the development of photocatalyst that utilise atmospheric oxygen as an oxidant for the valorisation of sugars, cellulose, hemicellulose etc. components. Initial focus will be on the design of homogeneous photocatalysts which are more selective than the heterogeneous one. Later, homogeneous catalysts will be transformed into heterogeneous one by using solid support onto it or synthesizing them separately. Finally, mechanistic studies such as DFT calculations, EPR studies, and in situ spectroscopic experiments will be conducted to understand the reaction mechanism.

Researcher(s)

• Promoter: Das Shoubhik
• Promoter: Maes Bert
• Co-promoter: Das Shoubhik
• Fellow: Zhang Tong

Research team(s)

• Organic synthesis (ORSY)

Project type(s)

• Research Project

Abstract

Carbon dioxide (CO2) is an abundant, safe and renewable carbon source and therefore an attractive C1 building block for the formation of organic molecules. The goal of this project is to design and synthesis of catalysts for the valorization of CO2 into valuable compounds.

Researcher(s)

• Promoter: Das Shoubhik

Research team(s)

• Organic synthesis (ORSY)

Project type(s)

• Research Project

Abstract

The main research objective in the University of Antwerp will be to develop novel metal-free heterogeneous photocatalysts for the activation of oxygen and later to find their application in organic synthesis. Especially, the hydroxylation reactions via functionalization of C-H bonds at the benzylic position is quite promising. The catalysts for this reaction are recyclable and even utilize sunlight as the energy source. We have also observed that heterogeneous photocatalyst generated the reactive oxygen species (ROS) and these ROS can be further applied into different oxygenation reactions. We are interested to investigate the applications of this concept in the organic synthesis and furthermore, to apply in late-stage modifications of natural products and drug molecules in a single step. Finally, characterization of the heterogeneous catalysts and mechanistic studies will be investigated to examine the stability of the catalyst and to find the role in the reactions.

Researcher(s)

• Promoter: Das Shoubhik
• Fellow: Zhang Yu

Research team(s)

• Organic synthesis (ORSY)

Project website

Project type(s)

• Research Project

Abstract

In general, generation of formic acid is highly advantageous due to its hydrogen storage capability. It should be noted that efficient storage of H2 gas is a big challenge to implement hydrogen economy. Considering the kinetic stability at room temperature and of high hydrogen content in formic acid, it is an alternative solution. In fact, use of formic acid is very atom efficient since 100% of the stored hydrogen is available for catalytic storage. It is obvious that formic acid can be generated in many possible ways. For example by the hydrogenation of CO2 or photocatalytic conversion of CO2 etc. However, these methods are far away from reaching the practical target. In contrast, use of biomass as a source of formic acid is considered as the future target due to their wide availability and as a cheap resource. In fact, biomass accounts for over 10% of global primary energy supply and is the world's fourth largest source of energy (following oil, coal, and natural gas). Based on this information, we aim to develop novel heterogeneous photocatalysts for biomass conversion. It should be noted that photocatalysis are well-known for its excellent properties such as cleanliness and energy savings. Furthermore, our previous experience with biomass valorization, CO2-based chemistry and different aspects of photocatalysis will be helpful to earn success through this novel and powerful strategy. Additionally, the PhD student (who will work in this project) is well aware about photocatalysis, biomass conversion, catalytic transformations and has already published/submitted two articles in photocatalysis.

Researcher(s)

• Promoter: Das Shoubhik

Research team(s)

• Organic synthesis (ORSY)

Project website

Project type(s)

• Research Project

Abstract

Transformations of CO2 into carboxylic acids are ideal reactions due to the widespread application of carboxylic acid compounds in the chemical and pharmaceutical industries. In general, direct C-H bond or C-X (X= halides) functionalization would allow 'unfunctionalized' molecules to be converted into synthetic intermediates and perhaps more importantly, an existing functionality could be exploited or suppressed selectively, during the assembly of molecular complexity. The approach could also allow complex molecules, especially pharmaceuticals, to be prepared in fewer steps. This proposal is concerned with N-heterocyclic carbenes (NHCs) catalysed C–H/ C-X bond functionalization of organic molecules followed by the insertion of CO2 to afford carboxylic acids. I intend to develop general site-selective strategy that takes place under mild conditions. The catalysts developed will be used to functionalize a range of organic motifs including 'functionally challenging' molecules found in natural products and complex pharmaceutical agents.

Researcher(s)

• Promoter: Das Shoubhik
• Fellow: Sahoo Prakash Kumar
• Fellow: Zhang Tong

Research team(s)

• Organic synthesis (ORSY)

Project type(s)

• Research Project

Abstract

Renewable energy driven chemistry is necessary for the development of a sustainable economy. As a result, CO2 should not be regarded as a waste rather should be considered as a chemical feedstock. Converting this CO2 into useful chemicals and fuels will provide access to high-value products from a nontoxic, renewable, and low-cost resource. In fact, visible-light mediated CO2 transformations to fuels and fine chemicals have already been achieved to promote this concept. However, current methods use expensive and toxic reagents along with expensive transition metal catalysts. In contrast, transition metal-free catalysts and systems are cheaper in price, non-toxic in nature, use less carbon footprint, and are an interesting avenue to explore.

Researcher(s)

• Promoter: Das Shoubhik

Research team(s)

• Organic synthesis (ORSY)

Project type(s)

• Research Project

Abstract

Start up research Prof. Shoubhik Das.-----------------------------------------------------------------------------------------------------------------------------------------------------------------------

Researcher(s)

• Promoter: Das Shoubhik
• Promoter: Maes Bert

Research team(s)

• Organic synthesis (ORSY)

Project type(s)

• Research Project