Project description:Bimetallic tandem catalysts have emerged as a promising strategy to locally increase the CO flux during electrochemical CO2 reduction, so as to maximize the rate of conversion to C-C-coupled products. Considering this, a novel Cu/C-Ag nanostructured catalyst has been prepared by a redox replacement process, in which the ratio of the two metals can be tuned by the replacement time. An optimum Cu/Ag composition with similarly sized particles showed the highest CO2 conversion to C2+ products compared to non-Ag-modified gas-diffusion electrodes. Gas chromatography and in-situ Raman measurements in a CO2 gas diffusion cell suggest the formation of top-bound linear adsorbed *CO followed by consumption of CO in the successive cascade steps, as evidenced by the increasingνC-H bands. These findings suggest that two mechanisms operate simultaneously towards the production of HCO2 H and C-C-coupled products on the Cu/Ag bimetallic surface.
Project description:Copper-based tandem schemes have emerged as promising strategies to promote the formation of multi-carbon products in the electrocatalytic CO2 reduction reaction. In such approaches, the CO-generating component of the tandem catalyst increases the local concentration of CO and thereby enhances the intrinsic carbon-carbon (C-C) coupling on copper. However, the optimal characteristics of the CO-generating catalyst for maximizing the C2 production are currently unknown. In this work, we developed tunable tandem catalysts comprising iron porphyrin (Fe-Por), as the CO-generating component, and Cu nanocubes (Cucub) to understand how the turnover frequency for CO (TOFCO) of the molecular catalysts impacts the C-C coupling on the Cu surface. First, we tuned the TOFCO of the Fe-Por by varying the number of orbitals involved in the π-system. Then, we coupled these molecular catalysts with the Cucub and assessed the current densities and faradaic efficiencies. We discovered that all of the designed Fe-Por boost ethylene production. The most efficient Cucub/Fe-Por tandem catalyst was the one including the Fe-Por with the highest TOFCO and exhibited a nearly 22-fold increase in the ethylene selectivity and 100 mV positive shift of the onset potential with respect to the pristine Cucub. These results reveal that coupling the TOFCO tunability of molecular catalysts with copper nanocatalysts opens up new possibilities towards the development of Cu-based catalysts with enhanced selectivity for multi-carbon product generation at low overpotential.
Project description:Metal organic frameworks (MOFs) are attractive materials to generate multifunctional catalysts for the electrocatalytic reduction of CO2 to hydrocarbons. Here we report the synthesis of Cu and Zn modified Al-fumarate (Al-fum) MOFs, in which Zn promotes the selective reduction of CO2 to CO and Cu promotes CO reduction to oxygenates and hydrocarbons in an electrocatalytic cascade. Cu and Zn nanoparticles (NPs) were introduced to the Al-fum MOF by a double solvent method to promote in-pore metal deposition, and the resulting reduced Cu-Zn@Al-fum drop-cast on a hydrophobic gas diffusion electrode for electrochemical study. Cu-Zn@Al-fum is active for CO2 electroreduction, with the Cu and Zn loading influencing the product yields. The highest faradaic efficiency (FE) of 62% is achieved at -1.0 V vs. RHE for the conversion of CO2 into CO, HCOOH, CH4, C2H4 and C2H5OH, with a FE of 28% to CH4, C2H4 and C2H5OH at pH 6.8. Al-fum MOF is a chemically robust matrix to disperse Cu and Zn NPs, improving electrocatalyst lifetime during CO2 reduction by minimizing transition metal aggregation during electrode operation.
Project description:Ethylene is an ideal CO2 product in an electrocatalytic CO2 reduction reaction (CO2RR) with high economic value. This paper synthesised Al-doped octahedral Cu2O (Al-Cu2O) nanocrystal by a simple wet chemical method. The selectivity of CO2RR products was improved by doping Al onto the surface of octahedral Cu2O. The Al-Cu2O was used as an efficient electrocatalyst for CO2RR with selective ethylene production. The Al-Cu2O exhibited a high % Faradic efficiency (FEC2H4) of 44.9% at -1.23 V (vs. RHE) in CO2 saturated 0.1 M KHCO3 electrolyte. Charge transfer from the Al atom to the Cu atom occurs after Al doping in Cu2O, optimizing the electronic structure and facilitating CO2RR to ethylene production. The DFT calculation showed that the Al-Cu2O catalyst could effectively reduce the adsorption energy of the *CHCOH intermediate and promote the mass transfer of charges, thus improving the FEC2H4. After Al doping into Cu2O, the center of d orbitals shift positively, which makes the d-band closer to the Fermi level. Furthermore, the density of electronic states increases due to the interaction between Cu atoms and intermediates, thus accelerating the electrochemical CO2 reduction process. This work proved that the metal doping strategy can effectively improve the catalytic properties of Cu2O, thus providing a useful way for CO2 cycling and green production of C2H4.
Project description:Operando soft and hard X-ray spectroscopic techniques were used in combination with plane-wave density functional theory (DFT) simulations to rationalize the enhanced activities of Zn-containing Cu nanostructured electrocatalysts in the electrocatalytic CO2 hydrogenation reaction. We show that at a potential for CO2 hydrogenation, Zn is alloyed with Cu in the bulk of the nanoparticles with no metallic Zn segregated; at the interface, low reducible Cu(I)-O species are consumed. Additional spectroscopic features are observed, which are identified as various surface Cu(I) ligated species; these respond to the potential, revealing characteristic interfacial dynamics. Similar behavior was observed for the Fe-Cu system in its active state, confirming the general validity of this mechanism; however, the performance of this system deteriorates after successive applied cathodic potentials, as the hydrogen evolution reaction then becomes the main reaction pathway. In contrast to an active system, Cu(I)-O is now consumed at cathodic potentials and not reversibly reformed when the voltage is allowed to equilibrate at the open-circuit voltage; rather, only the oxidation to Cu(II) is observed. We show that the Cu-Zn system represents the optimal active ensembles with stabilized Cu(I)-O; DFT simulations rationalize this observation by indicating that Cu-Zn-O neighboring atoms are able to activate CO2, whereas Cu-Cu sites provide the supply of H atoms for the hydrogenation reaction. Our results demonstrate an electronic effect exerted by the heterometal, which depends on its intimate distribution within the Cu phase and confirms the general validity of these mechanistic insights for future electrocatalyst design strategies.
Project description:For steady electroconversion to value-added chemical products with high efficiency, electrocatalyst reconstruction during electrochemical reactions is a critical issue in catalyst design strategies. Here, we report a reconstruction-immunized catalyst system in which Cu nanoparticles are protected by a quasi-graphitic C shell. This C shell epitaxially grew on Cu with quasi-graphitic bonding via a gas-solid reaction governed by the CO (g) - CO2 (g) - C (s) equilibrium. The quasi-graphitic C shell-coated Cu was stable during the CO2 reduction reaction and provided a platform for rational material design. C2+ product selectivity could be additionally improved by doping p-block elements. These elements modulated the electronic structure of the Cu surface and its binding properties, which can affect the intermediate binding and CO dimerization barrier. B-modified Cu attained a 68.1% Faradaic efficiency for C2H4 at -0.55 V (vs RHE) and a C2H4 cathodic power conversion efficiency of 44.0%. In the case of N-modified Cu, an improved C2+ selectivity of 82.3% at a partial current density of 329.2 mA/cm2 was acquired. Quasi-graphitic C shells, which enable surface stabilization and inner element doping, can realize stable CO2-to-C2H4 conversion over 180 h and allow practical application of electrocatalysts for renewable energy conversion.
Project description:The development of efficient catalysts is one of the main challenges in CO2 conversion to valuable chemicals and fuels. Herein, inspired by the knowledge of the thermocatalytic (TC) processes, Cu/ZnO and bare Cu catalysts enriched with Cu+1 were studied to convert CO2 via the electrocatalytic (EC) pathway. Integrating Cu with ZnO (a CO-generation catalyst) is a strategy explored in the EC CO2 reduction to reduce the kinetic barrier and enhance C-C coupling to obtain C2+ chemicals and energy carriers. Herein, ethanol was produced with the Cu/ZnO catalyst, reaching a productivity of about 5.27 mmol·gcat-1·h-1 in a liquid-phase configuration at ambient conditions. In contrast, bare copper preferentially produced C1 products like formate and methanol. During CO2 hydrogenation, a methanol selectivity close to 100% was achieved with the Cu/ZnO catalysts at 200 °C, a value that decreased at higher temperatures (i.e., 23% at 300 °C) because of thermodynamic limitations. The methanol productivity increased to approximately 1.4 mmol·gcat-1·h-1 at 300 °C. Ex situ characterizations after testing confirmed the potential of adding ZnO in Cu-based materials to stabilize the Cu1+/Cu0 interface at the electrocatalyst surface because of Zn and O enrichment by an amorphous zinc oxide matrix; while in the TC process, Cu0 and crystalline ZnO prevailed under CO2 hydrogenation conditions. It is envisioned that the lower *CO binding energy at the Cu0 catalyst surface in the TC process than in the Cu1+ present in the EC one leads to preferential CO and methanol production in the TC system. Instead, our EC results revealed that an optimum local CO production at the ZnO surface in tandem with a high amount of superficial Cu1+ + Cu0 species induces ethanol formation by ensuring an appropriate local amount of *CO intermediates and their further dimerization to generate C2+ products. Optimizing the ZnO loading on Cu is proposed to tune the catalyst surface properties and the formation of more reduced CO2 conversion products.
Project description:The electrochemical carbon dioxide reduction reaction (CO2RR) using copper (Cu)-based catalysts has received significant attention mainly because Cu is an element capable of producing hydrocarbons and oxygenates. One possible way to control the CO2RR performance at the electrode interface is by modifying catalysts with specific functional groups of different polymeric binders, which are necessary components in the process of electrode fabrication. However, the modification effect of the key functional groups on the CO2RR activity and selectivity is poorly understood over Cu-based catalysts. In this work, the role of functional groups (e.g., -COOH and -CF2 groups) in hydrophilic and hydrophobic polymeric binders on the CO2RR of Cu-based catalysts is investigated using a combination of electrochemical measurements, in situ characterization, and density functional theory (DFT) calculations. DFT results reveal that functional groups influence the binding energies of key intermediates involved in both CO2RR and the competing hydrogen evolution reaction, consistent with experimental observation of binder-dependent product distributions among formic acid, CO, CH4, and H2. This study provides a fundamental understanding that the selection of desired polymeric binders is a useful strategy for tuning the CO2RR activity and selectivity.
Project description:Electrochemical promotion of catalysis (EPOC) has been shown to accelerate the rate of many heterogeneous catalytic reactions; however, it has rarely been reported in low-temperature aqueous electrochemical reactions. Herein, we report a significant EPOC effect for the CO2 reduction to generate formate over Pd nanoparticles (NPs) in a 1 M KHCO3 aqueous solution. By applying a negative potential over differently-sized Pd NPs, the rate of formate production is greatly improved as compared to that at an open-circuit voltage, with a rate enhancement ratio ranging from 10 to 143. The thermocatalytic and electrocatalytic reduction of CO2 compete with each other and are promoted by the applied negative potential and H2 in the feeds, respectively. Inspired by the EPOC effect, a composite electrode containing Pd/C and Pt/C catalysts on different sides of a carbon paper was constructed for catalyzing the CO2 reduction without adding H2 to the feeds. Water electrolysis over Pt NPs generates H2, which then effectively promotes formate production over Pd NPs.
Project description:Development of cost effective and efficient electrocatalysts is crucial to generate H2 as an alternative source of energy. However, expensive noble metal based electrocatalysts show best electrocatalytic performances which acts as main bottle-neck for commercial application. Therefore, non-precious electrocatalysts have become important for hydrogen and oxygen evolution reactions. Herein, we report the synthesis of high surface area (35 m2/g) sodium niobate nanoparticles by citrate precursor method. These nanoparticles were characterized by different techniques like X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. Electrocatalytic properties of cost-effective sodium niobate nanoparticles were investigated for HER and OER in 0.5 M KOH electrolyte using Ag/AgCl as reference electrode. The sodium niobate electrode showed significant current density for both OER (≈2.7 mA/cm2) and HER (≈0.7 mA/cm2) with onset potential of 0.9 V for OER and 0.6 V for HER. As-prepared sodium niobate nanoparticles show enhanced photocatalytic property (86% removal) towards the degradation of rose Bengal dye. Dielectric behaviour at different sintering temperatures was explained by Koop's theory and Maxwell-Wagner mechanism. The dielectric constants of 41 and 38.5 and the dielectric losses of 0.04 and 0.025 were observed for the samples sintered at 500 °C and 700 °C, respectively at 500 kHz. Conductivity of the samples was understood by using power law fit.