Conversion of Polyethylene Waste into Gaseous Hydrocarbons via Integrated Tandem Chemical-Photo/Electrocatalytic Processes.

The chemical inertness of polyethylene makes chemical recycling challenging and motivates the development of new catalytic innovations to mitigate polymer waste. Current chemical recycling methods yield a complex mixture of liquid products, which is challenging to utilize in subsequent processes. Here, we present an oxidative depolymerization step utilizing diluted nitric acid to convert polyethylene into organic acids (40% organic acid yield), which can be coupled to a photo- or electrocatalytic decarboxylation reaction to produce hydrocarbons (individual hydrocarbon yields of 3 and 20%, respectively) with H2 and CO2 as gaseous byproducts. The integrated tandem process allows for the direct conversion of polyethylene into gaseous hydrocarbon products with an overall hydrocarbon yield of 1.0% for the oxidative/photocatalytic route and 7.6% for the oxidative/electrolytic route. The product selectivity is tunable with photocatalysis using TiO2 or carbon nitride, yielding alkanes (ethane and propane), whereas electrocatalysis on carbon electrodes produces alkenes (ethylene and propylene). This two-step recycling process of plastics can use sunlight or renewable electricity to convert polyethylene into valuable, easily separable, gaseous platform chemicals

Hydrogen Bubble Templated Metal Foams as Efficient Catalysts of CO 2 Electroreduction

The creation of open porous structures with an extremely high surface area is of great technological relevance. The electrochemical deposition of metal foams around co-generated hydrogen bubbles that act as templates for the deposition is a promising, cheap and simple approach to the fabrication of new electrocatalyst materials. Metal foams obtained by dynamic hydrogen bubble templating (DHBT) offer an intrinsically high electrical conductance with an open porous structure that enables the fast transport of gases and liquids. As an additional benefit, the confined space within the pores of DHBT metal foams may act as small reactors that can harbour reactions not possible at an open electrode interface. The number, distribution, and size of the pores can be fine-tuned by an appropriate choice of the electrolysis parameters so that metal foam catalysts prepared by the DHBT technique meet certain requirements. In this paper, we review the preparation of certain metal foams, and their applications as catalysts for the electrochemical reduction of CO

Morphology Matters: Tuning the Product Distribution of CO 2 Electroreduction on Oxide-Derived Cu Foam Catalysts

Mesoporous Cu foams formed by a template-assisted electrodeposition process have been identified as CO2 electrocatalysts that are highly selective toward C2 product formation (C2H4 and C2H6) with C2 efficiencies (FEC2) reaching 55%. The partial current of C2 product formation was found to be higher than that of the (parasitic) hydrogen evolution reaction (HER) at any potential studied (−0.4 to −1.0 vs the reversible hydrogen electrode). Moreover, formate production could largely be suppressed at any applied potential down to efficiencies (FEformate) of ≤6%. A key point of the Cu foam catalyst activation is the in operando reduction of a Cu2O phase, thereby creating a large abundance of surface sites active for C–C coupling. The cuprous oxide phase has been formed after the Cu electrodeposition step by exposing the large-surface area catalyst to air at room temperature. The superior selectivity of the Cu foam catalyst studied herein originates from a combination of two effects, the availability of specific surface sites for C–C coupling [dominant (100) surface texture] and the temporal trapping of gaseous intermediates (in particular CO and C2H4) inside the mesoporous catalyst material during CO2 electrolysis. A systematic CO2 electrolysis study reveals a strong dependence of the C2 efficiencies on the particular surface pore size of the mesoporous Cu catalysts with a maximal FEC2 between 50 and 100 μm pore diameters

Monitoring the Chemical State of Catalysts for CO 2 Electroreduction: An In Operando Study

A major concern of electrocatalysis research is to assess the structural and chemical changes that a catalyst may itself undergo in the course of the catalyzed process. These changes can influence not only the activity of the studied catalyst but also its selectivity toward the formation of a certain product. An illustrative example is the electroreduction of carbon dioxide on tin oxide nanoparticles, where under the operating conditions of the electrolysis (that is, at cathodic potentials), the catalyst undergoes structural changes which, in an extreme case, involve its reduction to metallic tin. This results in a decreased Faradaic efficiency (FE) for the production of formate (HCOO–) that is otherwise the main product of CO2 reduction on SnOx surfaces. In this study, we utilized potential- and time-dependent in operando Raman spectroscopy in order to monitor the oxidation state changes of SnO2 that accompany CO2 reduction. Investigations were carried out at different alkaline pH levels, and a strong correlation between the oxidation state of the surface and the FE of HCOO– formation was found. At moderately cathodic potentials, SnO2 exhibits a high FE for the production of formate, while at very negative potentials the oxide is reduced to metallic Sn, and the efficiency of formate production is significantly decreased. Interestingly, the highest FE of formate production is measured at potentials where SnO2 is thermodynamically unstable; however, its reduction is kinetically hindered

Oxo-functionalised mesoionic NHC nickel complexes for selective electrocatalytic reduction of CO 2 to formate

International audienceStrategies for the conversion of CO2 to valuable products are paramount for reducing the environmental risks associated with high levels of this greenhouse gas and offer unique opportunities for transforming waste into useful products. While catalysts based on nickel as an Earth-abundant metal for the sustainable reduction of CO2 are known, the vast majority produce predominantly CO as a product. Here, efficient and selective CO2 reduction to formate as a synthetically valuable product has been accomplished with novel nickel complexes containing a tailored C,O-bidentate chelating mesoionic carbene ligand. These nickel(II) complexes are easily accessible and show excellent catalytic activity for electrochemical H+ reduction to H2 (from HOAc in MeCN), and CO2 reduction (from CO2-saturated MeOH/MeCN solution) with high faradaic efficiency to yield formate exclusively as an industrially and synthetically valuable product from CO2. The most active catalyst precursor features the 4,6-di-tert-butyl substituted phenolate triazolylidene ligand, tolerates different proton donors including water, and reaches an unprecedented faradaic efficiency of 83% for formate production, constituting the most active and selective Ni-based system known to date for converting CO2 into formate as an important commodity chemical

Suppression of the Hydrogen Evolution Reaction Is the Key: Selective Electrosynthesis of Formate from CO 2 over Porous In 55 Cu 45 Catalysts

Direct electrosynthesis of formate through CO2 electroreduction (denoted CO2RR) is currently attracting great attention because formate is a highly valuable commodity chemical that is already used in a wide range of applications (e.g., formic acid fuel cells, tanning, rubber production, preservatives, and antibacterial agents). Herein, we demonstrate highly selective production of formate through CO2RR from a CO2-saturated aqueous bicarbonate solution using a porous In55Cu45 alloy as the electrocatalyst. This novel high-surface-area material was produced by means of an electrodeposition process utilizing the dynamic hydrogen bubble template approach. Faradaic efficiencies (FEs) of formate production (FEformate) never fell below 90% within a relatively broad potential window of approximately 400 mV, ranging from −0.8 to −1.2 V vs the reversible hydrogen electrode (RHE). A maximum FEformate of 96.8%, corresponding to a partial current density of jformate = −8.9 mA cm–2, was yielded at −1.0 V vs RHE. The experimental findings suggested a CO2RR mechanism involving stabilization of the HCOO* intermediate on the In55Cu45 alloy surface in combination with effective suppression of the parasitic hydrogen evolution reaction. What makes this CO2RR alloy catalyst particularly valuable is its stability against degradation and chemical poisoning. An almost constant formate efficiency of ∼94% was maintained in an extended 30 h electrolysis experiment, whereas pure In film catalysts (the reference benchmark system) showed a pronounced decrease in formate efficiency from 82% to 50% under similar experimental conditions. The identical location scanning electron microscopy approach was applied to demonstrate the structural stability of the applied In55Cu45 alloy foam catalysts at various length scales. We demonstrate that the proposed catalyst concept could be transferred to technically relevant support materials (e.g., carbon cloth gas diffusion electrode) without altering its excellent figures of merit

Dataset for "Integrated capture and solar-driven utilization of CO2 from flue gas and air"

The dataset contains raw data supporting the article ‘Integrated Capture and Solar-driven Utilization of CO2 from Flue Gas and Air’. An integrated photoelectrochemical system has been developed for sunlight-driven captured CO2 conversion coupled to waste plastic reforming. The dataset is divided into four key parts: i) Catalyst Characterization: contains SEM-EDX, IR, UV-Vis data, ii) CO2 Capture: contains NMR data, iii) Electrochemistry: contains all electrochemical data, iv) Photo-electrochemistry: contains all photoelectrochemical data. For more details about experimental procedure, instrumentation, and data collection, see the manuscript