RESUMO
The electrochemical reduction of nitrate (NO3-) and nitrite (NO2-) enables sustainable, carbon-neutral, and decentralized routes to produce ammonia (NH3). Copper-based materials are promising electrocatalysts for NOx- conversion to NH3. However, the underlying reaction mechanisms and the role of different Cu species during the catalytic process are still poorly understood. Herein, by combining quasi in situ X-ray photoelectron spectroscopy (XPS) and operando X-ray absorption spectroscopy (XAS), we unveiled that Cu is mostly in metallic form during the highly selective reduction of NO3-/NO2- to NH3. On the contrary, Cu(I) species are predominant in a potential region where the two-electron reduction of NO3- to NO2- is the major reaction. Electrokinetic analysis and in situ Raman spectroscopy was also used to propose possible steps and intermediates leading to NO2- and NH3, respectively. This work establishes a correlation between the catalytic performance and the dynamic changes of the chemical state of Cu, and provides crucial mechanistic insights into the pathways for NO3-/NO2- electrocatalytic reduction.
RESUMO
Bimetallic transition-metal oxides, such as spinel-like CoxFe3-xO4 materials, are known as attractive catalysts for the oxygen evolution reaction (OER) in alkaline electrolytes. Nonetheless, unveiling the real active species and active states in these catalysts remains a challenge. The coexistence of metal ions in different chemical states and in different chemical environments, including disordered X-ray amorphous phases that all evolve under reaction conditions, hinders the application of common operando techniques. Here, we address this issue by relying on operando quick X-ray absorption fine structure spectroscopy, coupled with unsupervised and supervised machine learning methods. We use principal component analysis to understand the subtle changes in the X-ray absorption near-edge structure spectra and develop an artificial neural network to decipher the extended X-ray absorption fine structure spectra. This allows us to separately track the evolution of tetrahedrally and octahedrally coordinated species and to disentangle the chemical changes and several phase transitions taking place in CoxFe3-xO4 catalysts and on their active surface, related to the conversion of disordered oxides into spinel-like structures, transformation of spinels into active oxyhydroxides, and changes in the degree of spinel inversion in the course of the activation treatment and under OER conditions. By correlating the revealed structural changes with the distinct catalytic activity for a series of CoxFe3-xO4 samples, we elucidate the active species and OER mechanism.
RESUMO
The activity of Ni (hydr)oxides for the electrochemical evolution of oxygen (OER), a key component of the overall water splitting reaction, is known to be greatly enhanced by the incorporation of Fe. However, a complete understanding of the role of cationic Fe species and the nature of the catalyst surface under reaction conditions remains unclear. Here, using a combination of electrochemical cell and conventional transmission electron microscopy, we show how the surface of NiO electrocatalysts, with initially well-defined surface facets, restructures under applied potential and forms an active NiFe layered double (oxy)hydroxide (NiFe-LDH) when Fe3+ ions are present in the electrolyte. Continued OER under these conditions, however, leads to the creation of additional FeOx aggregates. Electrochemically, the NiFe-LDH formation correlates with a lower onset potential toward the OER, whereas the formation of the FeOx aggregates is accompanied by a gradual decrease in the OER activity. Complementary insight into the catalyst near-surface composition, structure, and chemical state is further extracted using X-ray photoelectron spectroscopy, operando Raman spectroscopy, and operando X-ray absorption spectroscopy together with measurements of Fe uptake by the electrocatalysts using time-resolved inductively coupled plasma mass spectrometry. Notably, we identified that the catalytic deactivation under stationary conditions is linked to the degradation of in situ-created NiFe-LDH. These insights exemplify the complexity of the active state formation and show how its structural and morphological evolution under different applied potentials can be directly linked to the catalyst activation and degradation.
RESUMO
Spinel-type catalysts are promising anode materials for the alkaline oxygen evolution reaction (OER), exhibiting low overpotentials and providing long-term stability. In this study, we compared two structurally equal Co2FeO4 spinels with nominally identical stoichiometry and substantially different OER activities. In particular, one of the samples, characterized by a metastable precatalyst state, was found to quickly achieve its steady-state optimum operation, while the other, which was initially closer to the ideal crystallographic spinel structure, never reached such a state and required 168 mV higher potential to achieve 1 mA/cm2. In addition, the enhanced OER activity was accompanied by a larger resistance to corrosion. More specifically, using various ex situ, quasi in situ, and operando methods, we could identify a correlation between the catalytic activity and compositional inhomogeneities resulting in an X-ray amorphous Co2+-rich minority phase linking the crystalline spinel domains in the as-prepared state. Operando X-ray absorption spectroscopy revealed that these Co2+-rich domains transform during OER to structurally different Co3+-rich domains. These domains appear to be crucial for enhancing OER kinetics while exhibiting distinctly different redox properties. Our work emphasizes the necessity of the operando methodology to gain fundamental insight into the activity-determining properties of OER catalysts and presents a promising catalyst concept in which a stable, crystalline structure hosts the disordered and active catalyst phase.
RESUMO
Electrochemical CO2 reduction is a potential approach to convert CO2 into valuable chemicals using electricity as feedstock. Abundant and affordable catalyst materials are needed to upscale this process in a sustainable manner. Nickel-nitrogen-doped carbon (Ni-N-C) is an efficient catalyst for CO2 reduction to CO, and the single-site Ni-Nx motif is believed to be the active site. However, critical metrics for its catalytic activity, such as active site density and intrinsic turnover frequency, so far lack systematic discussion. In this work, we prepared a set of covalent organic framework (COF)-derived Ni-N-C catalysts, for which the Ni-Nx content could be adjusted by the pyrolysis temperature. The combination of high-angle annular dark-field scanning transmission electron microscopy and extended X-ray absorption fine structure evidenced the presence of Ni single-sites, and quantitative X-ray photoemission addressed the relation between active site density and turnover frequency.
RESUMO
In this study, we have taken advantage of a pulsed CO2 electroreduction reaction (CO2RR) approach to tune the product distribution at industrially relevant current densities in a gas-fed flow cell. We compared the CO2RR selectivity of Cu catalysts subjected to either potentiostatic conditions (fixed applied potential of -0.7 VRHE) or pulsed electrolysis conditions (1 s pulses at oxidative potentials ranging from Ean = 0.6 to 1.5 VRHE, followed by 1 s pulses at -0.7 VRHE) and identified the main parameters responsible for the enhanced product selectivity observed in the latter case. Herein, two distinct regimes were observed: (i) for Ean = 0.9 VRHE we obtained 10% enhanced C2 product selectivity (FEC2H4 = 43.6% and FEC2H5OH = 19.8%) in comparison to the potentiostatic CO2RR at -0.7 VRHE (FEC2H4 = 40.9% and FEC2H5OH = 11%), (ii) while for Ean = 1.2 VRHE, high CH4 selectivity (FECH4 = 48.3% vs 0.1% at constant -0.7 VRHE) was observed. Operando spectroscopy (XAS, SERS) and ex situ microscopy (SEM and TEM) measurements revealed that these differences in catalyst selectivity can be ascribed to structural modifications and local pH effects. The morphological reconstruction of the catalyst observed after pulsed electrolysis with Ean = 0.9 VRHE, including the presence of highly defective interfaces and grain boundaries, was found to play a key role in the enhancement of the C2 product formation. In turn, pulsed electrolysis with Ean = 1.2 VRHE caused the consumption of OH- species near the catalyst surface, leading to an OH-poor environment favorable for CH4 production.
RESUMO
The electrochemical reduction of carbon dioxide (CO2) powered by renewable energy is an attractive sustainable approach to mitigate CO2 emissions and to produce fuels or value-added chemicals. In order to tackle the challenges related to selectivity, activity, overpotential and durability, transition metal-based catalysts have been widely investigated in the last decades. In an effort to bridge the gap between the fields of homogeneous and heterogeneous catalysis, this review aims to survey the main strategies explored for the rational design of a wide variety of different metal catalysts, ranging from molecular systems to single-atom and nanostructured catalysts. Transition metal complexes containing heme and non-heme ligands have been selected to discuss the recent advances in the understanding of the structure-function relationship in molecular homogeneous catalysis as well as to summarize the main approaches proposed for the heterogenization or confinement of molecular catalysts on conductive surfaces. The main strategies to minimize catalyst cost are also presented, leading to atomically dispersed molecular-like M-Nx moieties embedded on 2D conducting materials. The superior performances of single-atom catalysts (SACs) and the structural similarity with their molecular analogs, suggest that transition metal catalysts containing well-defined sites may be intrinsically more active and selective towards CO2 conversion than the bulk heterogeneous materials. Finally, design approaches for metal nanoparticles (NPs) based on size, shape, and support tuning are summarized and compared to novel strategies based on the interaction with surface-bonded organic molecules. The studies herein presented show that the basic principles in molecular catalysis and organometallic chemistry can be effectively used to design new efficient and selective heterogeneous catalysts for CO2 reduction.
RESUMO
Direct conversion of carbon dioxide into multicarbon liquid fuels by the CO2 electrochemical reduction reaction (CO2 RR) can contribute to the decarbonization of the global economy. Here, well-defined Cu2 O nanocubes (NCs, 35â nm) uniformly covered with Ag nanoparticles (5â nm) were synthesized. When compared to bare Cu2 Oâ NCs, the catalyst with 5â at %â Ag on Cu2 Oâ NCs displayed a two-fold increase in the Faradaic efficiency for C2+ liquid products (30 % at -1.0â VRHE ), including ethanol, 1-propanol, and acetaldehyde, while formate and hydrogen were suppressed. Operando X-ray absorption spectroscopy revealed the partial reduction of Cu2 O during CO2 RR, accompanied by a reaction-driven redispersion of Ag on the CuOx â NCs. Data from operando surface-enhanced Raman spectroscopy further uncovered significant variations in the CO binding to Cu, which were assigned to Ag-Cu sites formed during CO2 RR that appear crucial for the C-C coupling and the enhanced yield of liquid products.
RESUMO
Bimetallic CuZn catalysts have been recently proposed as alternatives in order to achieve selectivity control during the electrochemical reduction of CO2 (CO2RR). However, fundamental understanding of the underlying reaction mechanism and parameters determining the CO2RR performance is still missing. In this study, we have employed size-controlled (â¼5 nm) Cu100-xZnx nanoparticles (NPs) supported on carbon to investigate the correlation between their structure and composition and catalytic performance. By tuning the concentration of Zn, a drastic increase in CH4 selectivity [â¼70% Faradaic efficiency (F.E.)] could be achieved for Zn contents from 10 to 50, which was accompanied by a suppression of the H2 production. Samples containing a higher Zn concentration displayed significantly lower CH4 production and an abrupt switch in the selectivity to CO. Lack of metal leaching was observed based on quasi in situ X-ray photoelectron spectroscopy (XPS). Operando X-ray absorption fine structure (XAFS) spectroscopy measurements revealed that the alloying of Cu atoms with Zn atoms takes place under reaction conditions and plays a determining role in the product selectivity. Time-dependent XAFS analysis showed that the local structure and chemical environment around the Cu atoms continuously evolve during CO2RR for several hours. In particular, cationic Zn species initially present were found to get reduced as the reaction proceeded, leading to the formation of a CuZn alloy (brass). The evolution of the Cu-Zn interaction with time during CO2RR was found to be responsible for the change in the selectivity from CH4 over Cu-ZnO NPs to CO over CuZn alloy NPs. This study highlights the importance of having access to in depth information on the interplay between the different atomic species in bimetallic NP electrocatalysts under operando reaction conditions in order to understand and ultimately tune their reactivity.
RESUMO
We explored the size-dependent activity and selectivity of Zn nanoparticles (NPs) for the electrochemical CO2 reduction reaction (CO2RR). Zn NPs ranging from 3 to 5 nm showed high activity and selectivity (â¼70%) for CO production, whereas those above 5 nm exhibited bulk-like catalytic properties. In addition, a drastic increase in hydrogen production was observed for the Zn NPs below 3 nm, which is associated with the enhanced content of low-coordinated sites on small NPs. The presence of residual cationic Zn species in the catalysts was also revealed during CO2RR via operando X-ray absorption fine-structure spectroscopy measurements. Such species are expected to play a role in the selectivity trends obtained. Our findings can serve as guidance for the development of highly active and CO-selective Zn-based catalysts for CO2RR.
RESUMO
Synthetic pentlandite (Fe4.5Ni4.5S8) is a promising electrocatalyst for hydrogen evolution, demonstrating high current densities, low overpotential, and remarkable stability in bulk form. The depletion of sulfur from the surface of this catalyst during the electrochemical reaction has been proposed to be beneficial for its catalytic performance, but the role of sulfur vacancies and the mechanism determining the reaction kinetics are still unknown. We have performed electrochemical operando studies of the vibrational dynamics of pentlandite under hydrogen evolution reaction conditions using 57Fe nuclear resonant inelastic X-ray scattering. Comparing the measured Fe partial vibrational density of states with density functional theory calculations, we have demonstrated that hydrogen atoms preferentially occupy substitutional positions replacing pre-existing sulfur vacancies. Once all vacancies are filled, the protonation proceeds interstitially, which slows down the reaction. Our results highlight the beneficial role of sulfur vacancies in the electrocatalytic performance of pentlandite and give insights into the hydrogen adsorption mechanism during the reaction.
RESUMO
Efficient, stable catalysts with high selectivity for a single product are essential if electroreduction of CO2 is to become a viable route to the synthesis of industrial feedstocks and fuels. A plasma oxidation pre-treatment of silver foil enhances the number of low-coordinated catalytically active sites, which dramatically lowers the overpotential and increases the activity of CO2 electroreduction to CO. At -0.6â V versus RHE more than 90 % Faradaic efficiency towards CO was achieved on a pre-oxidized silver foil. While transmission electron microscopy (TEM) and operando X-ray absorption spectroscopy showed that oxygen species can survive in the bulk of the catalyst during the reaction, quasi inâ situ X-ray photoelectron spectroscopy showed that the surface is metallic under reaction conditions. DFT calculations reveal that the defect-rich surface of the plasma-oxidized silver foils in the presence of local electric fields drastically decrease the overpotential of CO2 electroreduction.
RESUMO
Selective electrochemical reduction of CO2 is one of the most sought-after processes because of the potential to convert a harmful greenhouse gas to a useful chemical. We have discovered that immobilized Ag nanoparticles supported on carbon exhibit enhanced Faradaic efficiency and a lower overpotential for selective reduction of CO2 to CO. These electrocatalysts were synthesized directly on the carbon support by a facile one-pot method using a cysteamine anchoring agent resulting in controlled monodispersed particle sizes. These synthesized Ag/C electrodes showed improved activities, specifically decrease of the overpotential by 300 mV at 1 mA/cm(2), and 4-fold enhanced CO Faradaic efficiency at -0.75 V vs RHE with the optimal particle size of 5 nm compared to polycrystalline Ag foil. DFT calculations enlightened that the specific interaction between Ag nanoparticle and the anchoring agents modified the catalyst surface to have a selectively higher affinity to the intermediate COOH over CO, which effectively lowers the overpotential.
RESUMO
Pulsed CO2 electroreduction (CO2RR) has recently emerged as a facile way to in situ tune the product selectivity, in particular toward ethanol, without re-designing the catalytic system. However, in-depth mechanistic understanding requires comprehensive operando time-resolved studies to identify the kinetics and dynamics of the electrocatalytic interface. Here, we track the adsorbates and the catalyst state of pre-reduced Cu2O nanocubes ( ~ 30 nm) during pulsed CO2RR using sub-second time-resolved operando Raman spectroscopy. By screening a variety of product-steering pulse length conditions, we unravel the critical role of co-adsorbed OH and CO on the Cu surface next to the oxidative formation of Cu-Oad or CuOx/(OH)y species, impacting the kinetics of CO adsorption and boosting the ethanol selectivity. However, a too low OHad coverage following the formation of bulk-like Cu2O induces a significant increase in the C1 selectivity, while a too high OHad coverage poisons the surface for C-C coupling. Thus, we unveil the importance of co-adsorbed OH on the alcohol formation under CO2RR conditions and thereby, pave the way for improved catalyst design and operating conditions.
RESUMO
A key challenge in electrocatalysis remains controlling a catalyst's structural, chemical, and electrical properties under reaction conditions. While organic coatings showed promise for enhancing the selectivity and stability of catalysts for CO2 electroreduction (CO2RR), their impact on the chemical state of underlying metal electrodes has remained unclear. In this study, we show that organic thin films on polycrystalline copper (Cu) enable retaining Cu+ species at reducing potentials down to -1.0 V vs RHE, as evidenced by operando Raman and quasi in situ X-ray photoelectron spectroscopy. In situ electrochemical atomic force microscopy revealed the integrity of the porous organic film and nearly unaltered Cu electrode morphology. While the pristine thin film enhances the CO2-to-ethylene conversion, the addition of organic modifiers into electrolytes gives rise to improved CO2RR performance stability. Our findings showcase hybrid metal-organic systems as a versatile approach to control, beyond morphology and local environment, the oxidation states of catalysts and energy conversion materials.
RESUMO
Electrochemical CO2 reduction (CO2 RR) is a rising technology, aiming to reduce the energy sector dependence on fossil fuels and to produce carbon-neutral raw materials. Metal-nitrogen-doped carbons (M-N-C) are emerging, cost-effective catalysts for this reaction; however, their long-term stability is a major issue. To overcome this, understanding their structural evolution is crucial, requiring systematic in-depth operando studies. Here a series of M-N-C catalysts (M = Fe, Sn, Cu, Co, Ni, Zn) is investigated using operando X-ray absorption spectroscopy. It is found that the Fe-N-C and Sn-N-C are prone to oxide clusters formation even before CO2 RR. In contrast, the respective metal cations are singly dispersed in the as-prepared Cu-N-C, Co-N-C, Ni-N-C, and (Zn)-N-C. During CO2 RR, metallic clusters/nanoparticles reversibly formed in all catalysts, except for the Ni-N-C. This phenomenon, previously observed only in Cu-N-C, thus is ubiquitous in M-N-C catalysts. The competition between M-O and M-N interactions is an important factor determining the mobility of metal species in M-N-C. Specifically, the strong interaction between the Ni centers and the N-functional groups of the carbon support results in higher stability of the Ni single-sites, leading to the excellent performance of Ni-N-C in the CO2 to CO conversion, in comparison to other transition metals.
RESUMO
Electrochemical reduction of CO2 (CO2RR) is an attractive technology to reintegrate the anthropogenic CO2 back into the carbon cycle driven by a suitable catalyst. This study employs highly efficient multi-carbon (C2+) producing Cu2O nanocubes (NCs) decorated with CO-selective Au nanoparticles (NPs) to investigate the correlation between a high CO surface concentration microenvironment and the catalytic performance. Structure, morphology and near-surface composition are studied via operando X-ray absorption spectroscopy and surface-enhanced Raman spectroscopy, operando high-energy X-ray diffraction as well as quasi in situ X-ray photoelectron spectroscopy. These operando studies show the continuous evolution of the local structure and chemical environment of our catalysts during reaction conditions. Along with its alloy formation, a CO-rich microenvironment as well as weakened average CO binding on the catalyst surface during CO2RR is detected. Linking these findings to the catalytic function, a complex compositional interplay between Au and Cu is revealed in which higher Au loadings primarily facilitate CO formation. Nonetheless, the strongest improvement in C2+ formation appears for the lowest Au loadings, suggesting a beneficial role of the Au-Cu atomic interaction for the catalytic function in CO2RR. This study highlights the importance of site engineering and operando investigations to unveil the electrocatalyst's adaptations to the reaction conditions, which is a prerequisite to understand its catalytic behavior.
RESUMO
The production of green hydrogen through alkaline water electrolysis is the key technology for the future carbon-neutral industry. Nanocrystalline Co3O4 catalysts are highly promising electrocatalysts for the oxygen evolution reaction and their activity strongly benefits from Fe surface decoration. However, limited knowledge of decisive catalyst motifs at the atomic level during oxygen evolution prevents their knowledge-driven optimization. Here, we employ a variety of operando spectroscopic methods to unveil how Fe decoration increases the catalytic activity of Co3O4 nanocatalysts as well as steer the (near-surface) active state formation. Our study shows a link of the termination-dependent Fe decoration to the activity enhancement and a significantly stronger Co3O4 near-surface (structural) adaptation under the reaction conditions. The near-surface Fe- and Co-O species accumulate an oxidative charge and undergo a reversible bond contraction during the catalytic process. Moreover, our work demonstrates the importance of low coordination surface sites on the Co3O4 host to ensure an efficient Fe-induced activity enhancement, providing another puzzle piece to facilitate optimized catalyst design.
RESUMO
Copper-based catalysts are established catalytic systems for the electrocatalytic CO2 reduction reaction (CO2RR), where the greenhouse gas CO2 is converted into valuable industrial chemicals, such as energy-dense C2+ products, using energy from renewable sources. However, better control over the catalyst selectivity, especially at industrially relevant high current density conditions, is needed to expedite the economic viability of the CO2RR. For this purpose, bimetallic materials, where copper is combined with a secondary metal, comprise a promising and a highly tunable catalyst for the CO2RR. Nevertheless, the synergy between copper and the selected secondary metal species, the evolution of the bimetallic structural motifs under working conditions and the effect of the secondary metal on the kinetics of the Cu redox behavior require careful investigation. Here, we employ operando quick X-ray absorption fine structure (QXAFS) spectroscopy coupled with machine-learning based data analysis and surface-enhanced Raman spectroscopy (SERS) to investigate the time-dependent chemical and structural changes in catalysts derived from shape-selected ZnO/Cu2O nanocubes under CO2RR conditions at current densities up to -500 mA cm-2. We furthermore relate the catalyst transformations observed under working conditions to the catalytic activity and selectivity and correlate potential-dependent surface and subsurface processes. We report that the addition of Zn to a Cu-based catalyst has a crucial impact on the kinetics of subsurface processes, while redox processes of the Cu surface layer remain largely unaffected. Interestingly, the presence of Zn was found to contribute to the stabilization of cationic Cu(i) species, which is of catalytic relevance since Cu(0)/Cu(i) interfaces have been reported to be beneficial for efficient electrocatalytic CO2 conversion to complex multicarbon products. At the same time, we attribute the increase of the C2+ product selectivity to the formation of Cu-rich CuZn alloys in samples with low Zn content, while Zn-rich alloy phases result in an increased formation of CO paralleled by an increase of the parasitic hydrogen evolution reaction.
RESUMO
Understanding the evolution of unique structural motifs in bimetallic catalysts under reaction conditions, and linking them to the observed catalytic properties is necessary for the rational design of the next generation of catalytic materials. Extended X-ray absorption fine structure (EXAFS) spectroscopy is a premier experimental method to address this issue, providing the possibility to track the changes in the structure of working catalysts. Unfortunately, the intrinsic heterogeneity and enhanced disorder characteristic of catalytic materials experiencing structural transformations under reaction conditions, as well as the low signal-to-noise ratio that is common for in situ EXAFS spectra hinder the application of conventional data analysis approaches. Here we address this problem by employing machine learning methods (artificial neural networks) to establish the relationship between EXAFS features and structural motifs in metals as well as oxide materials. We apply this approach to time-dependent EXAFS spectra acquired from copper-zinc nanoparticles during the electrochemical reduction of CO2 to reveal the details of the composition-dependent structural evolution and brass alloy formation, and their correlation with the catalytic selectivity of these materials.