Development of a single crystal sample holder for interfacing ultrahigh vacuum and electrochemical experimentation

Electrocatalyst surfaces prepared under ultrahigh vacuum (UHV) conditions can create model surfaces to better connect theoretical calculations with experimental studies. The development of a single crystal sample holder and inert electrochemical cells prepared with modularity and chemical stability in mind would allow for expensive single crystals to be reused indefinitely in both UHV and electrochemical settings. This sample holder shows reproducible surface preparations for single crystal samples and consistent electrochemical experiments without the introduction of impurities into the surface. The presented setup has been used as a critical piece for the characterization of Cu(111) surfaces under CO2 electrochemical reduction reaction conditions as a test case

Enhanced Formic Acid Oxidation over SnO₂-decorated Pd Nanocubes

The formic acid oxidation reaction (FAOR) is one of the key reactions that can be used at the anode of low-temperature liquid fuel cells. To allow the knowledge-driven development of improved catalysts, it is necessary to deeply understand the fundamental aspects of the FAOR, which can be ideally achieved by investigating highly active model catalysts. Here, we studied SnO2-decorated Pd nanocubes (NCs) exhibiting excellent electrocatalytic performance for formic acid oxidation in acidic medium with a SnO2 promotion that boosts the catalytic activity by a factor of 5.8, compared to pure Pd NCs, exhibiting values of 2.46 A mg–1Pd for SnO2@Pd NCs versus 0.42 A mg–1Pd for the Pd NCs and a 100 mV lower peak potential. By using ex situ, quasi in situ, and operando spectroscopic and microscopic methods (namely, transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption fine-structure spectroscopy), we identified that the initially well-defined SnO2-decorated Pd nanocubes maintain their structure and composition throughout FAOR. In situ Fourier-transformed infrared spectroscopy revealed a weaker CO adsorption site in the case of the SnO2-decorated Pd NCs, compared to the monometallic Pd NCs, enabling a bifunctional reaction mechanism. Therein, SnO2 provides oxygen species to the Pd surface at low overpotentials, promoting the oxidation of the poisoning CO intermediate and, thus, improving the catalytic performance of Pd. Our SnOx-decorated Pd nanocubes allowed deeper insight into the mechanism of FAOR and hold promise for possible applications in direct formic acid fuel cells

Steering the structure and selectivity of CO₂ electroreduction catalysts by potential pulses

Convoluted selectivity trends and a missing link between reaction product distribution and catalyst properties hinder practical applications of the electrochemical CO2 reduction reaction (CO2RR) for multicarbon product generation. Here we employ operando X-ray absorption and X-ray diffraction methods with subsecond time resolution to unveil the surprising complexity of catalysts exposed to dynamic reaction conditions. We show that by using a pulsed reaction protocol consisting of alternating working and oxidizing potential periods that dynamically perturb catalysts derived from Cu2O nanocubes, one can decouple the effect of the ensemble of coexisting copper species on the product distribution. In particular, an optimized dynamic balance between oxidized and reduced copper surface species achieved within a narrow range of cathodic and anodic pulse durations resulted in a twofold increase in ethanol production compared with static CO2RR conditions. This work thus prepares the ground for steering catalyst selectivity through dynamically controlled structural and chemical transformations

Structure- and Electrolyte-Sensitivity in CO₂ Electroreduction

The utilization of fossil fuels (i.e., coal, petroleum, and natural gas) as the main energy source gives rise to serious environmental issues, including global warming caused by the continuously increasing level of atmospheric CO2. To deal with this challenge, fossil fuels are being partially replaced by renewable energy such as solar and wind. However, such energy sources are usually intermittent and currently constitute a very low portion of the overall energy consumption. Recently, the electrochemical conversion of CO2 to chemicals and fuels with high energy density driven by electricity derived from renewable energy has been recognized as a promising strategy toward sustainable energy. The activation and reduction of CO2, which is a thermodynamically stable and kinetically inert molecule, is extremely challenging. Although the participation of protons in the CO2 electroreduction reaction (CO2RR) helps lower the energy barrier, high overpotentials are still needed to efficiently drive the process. On the other hand, the concurrent hydrogen evolution reaction (HER) under CO2RR conditions leads to lower selectivity toward CO2RR products. Electrocatalysts that are highly active and selective for multicarbon products are urgently needed to improve the energy efficiency of CO2RR. The reduction of CO2 involves multiple proton–electron transfers and has many complex intermediates. Recent reports have shown that the relative stability of the intermediates on the surface of catalysts determines final reaction pathways as well as the product selectivity. Furthermore, this reaction displays a strong structure-sensitivity. The atomic arrangement, electronic structure, chemical composition, and oxidation state of the catalysts significantly influence catalyst performance. Fundamental understanding of the dependence of the reaction mechanisms on the catalyst structure would guide the rational design of new nanostructured CO2RR catalysts. As a reaction proceeding in a complex environment containing gas/liquid/solid interfaces, CO2RR is also intensively affected by the electrolyte. The electrolyte composition in the near surface region of the electrode where the reaction takes place plays a vital role in the reactivity. However, the former might also be indirectly determined by the bulk electrolyte composition via diffusion. Adding to the complexity, the structure, chemical state and surface composition of the catalysts under reaction conditions usually undergo dynamic changes, especially when adsorbed ions are considered. Therefore, in addition to tuning the structure of the electrocatalysts, being able to also modify the electrolyte provides an alternative method to tune the activity and selectivity of CO2RR. In situ and operando characterization methods must be employed to gain in depth understanding on the structure- and electrolyte-sensitivity of real CO2RR catalysts under working conditions. This Account provides examples of recent advances in the development of nanostructured catalysts and mechanistic understanding of CO2RR. It discusses how the structure of a catalyst (crystal orientation, oxidation state, atomic arrangement, defects, size, surface composition, segregation, etc.) influences the activity and selectivity, and how the electrolyte also plays a determining role in the reaction activity and selectivity. Finally, the importance of in situ and operando characterization methods to understand the structure- and electrolyte-sensitivity of the CO2RR is discussed

Rational catalyst and electrolyte design for CO₂ electroreduction towards multicarbon products

The CO2 electroreduction reaction (CO2RR) to fuels and feedstocks is an attractive route to close the anthropogenic carbon cycle and store renewable energy. The generation of more reduced chemicals, especially multicarbon oxygenate and hydrocarbon products (C2+) with higher energy densities, is highly desirable for industrial applications. However, selective conversion of CO2 to C2+ suffers from a high overpotential, a low reaction rate and low selectivity, and the process is extremely sensitive to the catalyst structure and electrolyte. Here we discuss strategies to achieve high C2+ selectivity through rational design of the catalyst and electrolyte. Current state-of-the-art catalysts, including Cu and Cu–bimetallic catalysts, as well as some alternative materials, are considered. The importance of taking into consideration the dynamic evolution of the catalyst structure and composition are highlighted, focusing on findings extracted from in situ and operando characterizations. Additional theoretical insight into the reaction mechanisms underlying the improved C2+ selectivity of specific catalyst geometries and compositions in synergy with a well-chosen electrolyte are also provided

The role of in situ generated morphological motifs and Cu(I) species in C₂₊ product selectivity during CO₂ pulsed electroreduction

The efficient electrochemical conversion of CO2 provides a route to fuels and feedstocks. Copper catalysts are well-known to be selective to multicarbon products, although the role played by the surface architecture and the presence of oxides is not fully understood. Here we report improved efficiency towards ethanol by tuning the morphology and oxidation state of the copper catalysts through pulsed CO2 electrolysis. We establish a correlation between the enhanced production of C2+ products (76% ethylene, ethanol and n-propanol at −1.0 V versus the reversible hydrogen electrode) and the presence of (100) terraces, Cu2O and defects on Cu(100). We monitored the evolution of the catalyst morphology by analysis of cyclic voltammetry curves and ex situ atomic force microscopy data, whereas the chemical state of the surface was examined via quasi in situ X-ray photoelectron spectroscopy. We show that the continuous regeneration of defects and Cu(i) species synergistically favours C–C coupling pathways

Selective CO₂ Electroreduction to Ethylene and Multicarbon Alcohols via Electrolyte-Driven Nanostructuring

The production of multicarbon products (C2+) from CO2 electroreduction reaction (CO2RR) is highly desirable for storing renewable energy and reducing carbon emission. Here we report the electrochemical synthesis of CO2RR catalysts that are highly selective for C2+ products via electrolyte‐driven nanostructuring. Nanostructured Cu catalysts synthesized in the presence of specific anions can selectively convert CO2 to ethylene and multicarbon alcohols in aqueous 0.1 M KHCO3 solution, with the iodine‐modified catalyst displaying the highest Faradaic efficiency of ~80% and partial current density of ~31.2 mA cm-2 for C2+ products at −0.9 V vs RHE. Operando X‐ray absorption spectroscopy and quasi in situ X‐ray photoelectron spectroscopy measurements revealed that the high C2+ selectivity of these nanostructured Cu catalysts can be attributed to the highly roughened surface morphology induced by our synthesis, the presence of subsurface oxygen and Cu+ species, and the adsorbed halides. This work provides new insight into the parameters that should be tuned in order to rationally design C2+‐selective CO2RR catalysts

Selective CO₂ Electroreduction to Ethylene and Multicarbon Alcohols via Electrolyte-Driven Nanostructuring

The production of multicarbon products (C2+) from CO2 electroreduction reaction (CO2RR) is highly desirable for storing renewable energy and reducing carbon emission. Here we report the electrochemical synthesis of CO2RR catalysts that are highly selective for C2+ products via electrolyte‐driven nanostructuring. Nanostructured Cu catalysts synthesized in the presence of specific anions can selectively convert CO2 to ethylene and multicarbon alcohols in aqueous 0.1 M KHCO3 solution, with the iodine‐modified catalyst displaying the highest Faradaic efficiency of ~80% and partial current density of ~31.2 mA cm-2 for C2+ products at −0.9 V vs RHE. Operando X‐ray absorption spectroscopy and quasi in situ X‐ray photoelectron spectroscopy measurements revealed that the high C2+ selectivity of these nanostructured Cu catalysts can be attributed to the highly roughened surface morphology induced by our synthesis, the presence of subsurface oxygen and Cu+ species, and the adsorbed halides. This work provides new insight into the parameters that should be tuned in order to rationally design C2+‐selective CO2RR catalysts

Imaging electrochemically synthesized Cu₂O cubes and their morphological evolution under conditions relevant to CO₂ electroreduction

Catalytic selectivity during carbon dioxide electroreduction can be tuned by using geometric copper-based catalysts. Here, the authors use liquid cell transmission electron microscopy to study the in situ synthesis and morphological evolution Cu2O cubes under carbon dioxide electroreduction conditions