Contributions of heterogeneous catalysis enabling resource efficiency and circular economy.

Our industry today is predominantly based on linear value chains. Raw materials are extracted from primary sources, processed into products, used, and disposed of at the end of their life cycle. This linear economy causes a wide range of negative environmental impacts owing to the resulting greenhouse gas emissions and pollution of marine and terrestrial ecosystems. Closed carbon cycles and climate-neutral energy production are essential for the production not only of fuels but also of all chemicals, including plastics and fertilizers, to counteract climate change and further damage to the environment. In this regard, this article discusses the importance of heterogeneous catalysts for selected technologies associated with this transformation of the resource base and energy supply. It discusses the technological framework conditions of a net CO2-neutral industry, with a focus on electrocatalytic water-splitting for hydrogen production, as well as the catalytic challenges of production of chemicals for the whole value chain using biomass, CO2 and plastic waste as raw materials. This article is part of the discussion meeting issue 'Green carbon for the chemical industry of the future'.

Metallic Impurities in Electrolysis: Catalytic Effect of Pb Traces in Reductive Amination and Acetone Reduction.

The electrochemical hydrogenation (e-hydrogenation) of unsaturated compounds like imines or carbonyls presents a benign reduction method. It enables direct use of electrons as reducing agent, water as proton source, while bypassing the need for elevated temperatures or pressures. In this contribution, we discuss the nature of active sites in electrocatalytic reductive amination with the transformation of acetone and methylamine as model reaction. Surprisingly, lead impurities in the ppm-range proved to possess a significant effect in e-hydrogenation. Accordingly, the influence of applied potential and cathode material in presence of 1 ppm Pb was investigated. Finally, we transferred the insights to the reduction of acetone manifesting comparable observations as for imine reduction. The results suggest that previous studies on electrochemical reduction in the presence of lead electrodes should be re-evaluated.

Origin of copper dissolution under electrocatalytic reduction conditions involving amines.

Cu dissolution has been identified as the dominant process that causes cathode degradation and losses even under cathodic conditions involving methylamine. Despite extensive experimental research, our fundamental and theoretical understanding of the atomic-scale mechanism for Cu dissolution under electrochemical conditions, eventually coupled with surface restructuring processes, is limited. Here, driven by the observation that the working Cu electrode is corroded using mixtures of acetone and methylamine even under reductive potential conditions (-0.75 V vs. RHE), we employed Grand Canonical density functional theory to understand this dynamic process under potential from a microscopic perspective. We show that amine ligands in solution directly chemisorb on the electrode, coordinate with the metal center, and drive the rearrangement of the copper surface by extracting Cu as adatoms in low coordination positions, where other amine ligands can coordinate and stabilize a surface copper-ligand complex, finally forming a detached Cu-amine cationic complex in solution, even under negative potential conditions. Calculations predict that dissolution would occur for a potential of -1.1 V vs. RHE or above. Our work provides a fundamental understanding of Cu dissolution facilitated by surface restructuring in amine solutions under electroreduction conditions, which is required for the rational design of durable Cu-based cathodes for electrochemical amination or other amine involving reduction processes.

In situ adsorption of itaconic acid from fermentations of Ustilago cynodontis improves bioprocess efficiency.

BACKGROUND: Reducing the costs of biorefinery processes is a crucial step in replacing petrochemical products by sustainable, biotechnological alternatives. Substrate costs and downstream processing present large potential for improvement of cost efficiency. The implementation of in situ adsorption as an energy-efficient product recovery method can reduce costs in both areas. While selective product separation is possible at ambient conditions, yield-limiting effects, as for example product inhibition, can be reduced in an integrated process. RESULTS: An in situ adsorption process was integrated into the production of itaconic acid with Ustilago cynodontis IAmax, as an example of a promising biorefinery process. A suitable feed strategy was developed to enable efficient production and selective recovery of itaconic acid by maintaining optimal glucose concentrations. Online monitoring via Raman spectroscopy was implemented to enable a first process control and understand the interactions of metabolites with the adsorbent. In the final, integrated bioprocess, yield, titre, and space-time yield of the fermentation process were increased to values of 0.41 gIA/gGlucose, 126.5 gIA/L and 0.52 gIA/L/h. This corresponds to an increase of up to 30% in comparison to the first extended batch experiment without in situ product removal. Itaconic acid was recovered with a purity of at least 95% and high concentrations above 300 g/L in the eluate. CONCLUSION: Integration of product separation via adsorption into the bioprocess was successfully conducted and improved the efficiency of itaconic acid production. Raman spectroscopy was proven to be a reliable tool for online monitoring of various metabolites and facilitated design and validation of the complex separation and feed process. The general process concept can be transferred to the production of various similar bioproducts, expanding the tool kit for design of innovative biorefinery processes.

Copper Site Motion Promotes Catalytic NOx Reduction under Zeolite Confinement.

Ammonia-mediated selective catalytic reduction (NH3-SCR) is currently the key approach to abate nitrogen oxides (NOx) emitted from heavy-duty lean-burn vehicles. The state-of-art NH3-SCR catalysts, namely, copper ion-exchanged chabazite (Cu-CHA) zeolites, perform rather poorly at low temperatures (below 200 °C) and are thus incapable of eliminating effectively NOx emissions under cold-start conditions. Here, we demonstrate a significant promotion of low-temperature NOx reduction by reinforcing the dynamic motion of zeolite-confined Cu sites during NH3-SCR. Combining complex impedance-based in situ spectroscopy (IS) and extended density-functional tight-binding molecular dynamics simulation, we revealed an environment- and temperature-dependent nature of the dynamic Cu motion within the zeolite lattice. Further coupling in situ IS with infrared spectroscopy allows us to unravel the critical role of monovalent Cu in the overall Cu mobility at a molecular level. Based on these mechanistic understandings, we elicit a boost of NOx reduction below 200 °C by reinforcing the dynamic Cu motion in various Cu-zeolites (Cu-CHA, Cu-ZSM-5, Cu-Beta, etc.) via facile postsynthesis treatments, either in a reductive mixture at low temperatures (below 250 °C) or in a nonoxidative atmosphere at high temperatures (above 450 °C).

Respiration-based investigation of adsorbent-bioprocess compatibility.

BACKGROUND: The efficiency of downstream processes plays a crucial role in the transition from conventional petrochemical processes to sustainable biotechnological production routes. One promising candidate for product separation from fermentations with low energy demand and high selectivity is the adsorption of the target product on hydrophobic adsorbents. However, only limited knowledge exists about the interaction of these adsorbents and the bioprocess. The bioprocess could possibly be harmed by the release of inhibitory components from the adsorbent surface. Another possibility is co-adsorption of essential nutrients, especially in an in situ application, making these nutrients unavailable to the applied microorganism. RESULTS: A test protocol investigating adsorbent-bioprocess compatibility was designed and applied on a variety of adsorbents. Inhibitor release and nutrient adsorption was studied in an isolated manner. Respiratory data recorded by a RAMOS device was used to assess the influence of the adsorbents on the cultivation in three different microbial systems for up to six different adsorbents per system. While no inhibitor release was detected in our investigations, adsorption of different essential nutrients was observed. CONCLUSION: The application of adsorption for product recovery from the bioprocess was proven to be generally possible, but nutrient adsorption has to be assessed for each application individually. To account for nutrient adsorption, adsorptive product separation should only be applied after sufficient microbial growth. Moreover, concentrations of co-adsorbed nutrients need to be increased to compensate nutrient loss. The presented protocol enables an investigation of adsorbent-bioprocess compatibility with high-throughput and limited effort.

Single-Atom Catalysts on Covalent Triazine Frameworks: at the Crossroad between Homogeneous and Heterogeneous Catalysis.

Heterogeneous single-site and single-atom catalysts potentially enable combining the high catalytic activity and selectivity of molecular catalysts with the easy continuous operation and recycling of solid catalysts. In recent years, covalent triazine frameworks (CTFs) found increasing attention as support materials for particulate and isolated metal species. Bearing a high fraction of nitrogen sites, they allow coordinating molecular metal species and stabilizing particulate metal species, respectively. Dependent on synthesis method and pretreatment of CTFs, materials resembling well-defined highly crosslinked polymers or materials comparable to structurally ill-defined nitrogen-containing carbons result. Accordingly, CTFs serve as model systems elucidating the interaction of single-site, single-atom and particulate metal species with such supports. Factors influencing the transition between molecular and particulate systems are discussed to allow deriving tailored catalyst systems.

Innovative Electrochemical Strategies for Hydrogen Production: From Electricity Input to Electricity Output.

Renewable H2 production by water electrolysis has attracted much attention due to its numerous advantages. However, the energy consumption of conventional water electrolysis is high and mainly driven by the kinetically inert anodic oxygen evolution reaction. An alternative approach is the coupling of different half-cell reactions and the use of redox mediators. In this review, we, therefore, summarize the latest findings on innovative electrochemical strategies for H2 production. First, we address redox mediators utilized in water splitting, including soluble and insoluble species, and the corresponding cell concepts. Second, we discuss alternative anodic reactions involving organic and inorganic chemical transformations. Then, electrochemical H2 production at both the cathode and anode, or even H2 production together with electricity generation, is presented. Finally, the remaining challenges and prospects for the future development of this research field are highlighted.

Finding the Sweet Spot of Photocatalysis─A Case Study Using Bipyridine-Based CTFs.

Covalent triazine frameworks (CTFs) are a class of porous organic polymers that continuously attract growing interest because of their outstanding chemical and physical properties. However, the control of extended porous organic framework structures at the molecular scale for a precise adjustment of their properties has hardly been achieved so far. Here, we present a series of bipyridine-based CTFs synthesized through polycondensation, in which the sequence of specific building blocks is well controlled. The reported synthetic strategy allows us to tailor the physicochemical features of the CTF materials, including the nitrogen content, the apparent specific surface area, and optoelectronic properties. Based on a comprehensive analytical investigation, we demonstrate a direct correlation of the CTF bipyridine content with the material features such as the specific surface area, band gap, charge separation, and surface wettability with water. The entirety of these parameters dictates the catalytic activity as demonstrated for the photocatalytic hydrogen evolution reaction (HER). The material with the optimal balance between optoelectronic properties and highest hydrophilicity enables HER production rates of up to 7.2 mmol/(h·g) under visible light irradiation and in the presence of a platinum cocatalyst.

Integrated Co-Electrolysis and Syngas Methanation for the Direct Production of Synthetic Natural Gas from CO2 and H2 O.

The concept of an integrated power-to-gas (P2G) process was demonstrated for renewable energy storage by converting renewable electrical energy to synthetic fuels. Such a dynamically integrated process enables direct production of synthetic natural gas (SNG) from CO2 and H2 O. The produced SNG can be stored or directly injected into the existing natural gas network. To study process integration, operating parameters of the high-temperature solid oxide electrolysis cell (SOEC) producing syngas (H2 +CO) mixtures through co-electrolysis and a fixed bed reactor for syngas methanation of such gas mixtures were first optimized individually. Reactor design, operating conditions, and enhanced SNG selectivity were the main targets of the study. SOEC experiments were performed on state-of-the-art button cells. Varying operating conditions (temperature, flow rate, gas mixture and current density) emphasized the capability of the system to produce tailor-made syngas mixtures for downstream methanation. Catalytic syngas methanation was performed using hydrotalcite-derived 20 %Ni-2 %Fe/(Mg,Al)Ox catalyst and commercial methanation catalyst (Ni/Al2 O3 ) as reference. Despite water in the feed mixture, SNG with high selectivity (≥90 %) was produced at 300 °C and atmospheric pressure. An adequate rate of syngas conversion was obtained with H2 O contents up to 30 %, decreasing significantly for 50 % H2 O in the feed. Compared to the commercial catalyst, 20 %Ni-2 %Fe/(Mg,Al)Ox enabled a higher rate of COx conversion.