Electrocatalytic Nitrate and Nitrite Reduction toward Ammonia Using Cu2O Nanocubes: Active Species and Reaction Mechanisms.

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.

Role of Fe decoration on the oxygen evolving state of Co3O4 nanocatalysts.

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.

Spatially and Chemically Resolved Visualization of Fe Incorporation into NiO Octahedra during the Oxygen Evolution Reaction.

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.

Deciphering the Structural and Chemical Transformations of Oxide Catalysts during Oxygen Evolution Reaction Using Quick X-ray Absorption Spectroscopy and Machine Learning.

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.

Covalent Organic Framework (COF) Derived Ni-N-C Catalysts for Electrochemical CO2 Reduction: Unraveling Fundamental Kinetic and Structural Parameters of the Active Sites.

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.

Selectivity Control of Cu Nanocrystals in a Gas-Fed Flow Cell through CO2 Pulsed Electroreduction.

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.

Operando Investigation of Ag-Decorated Cu2 O Nanocube Catalysts with Enhanced CO2 Electroreduction toward Liquid Products.

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, 35 nm) uniformly covered with Ag nanoparticles (5 nm) were synthesized. When compared to bare Cu2 O NCs, the catalyst with 5 at % Ag on Cu2 O NCs displayed a two-fold increase in the Faradaic efficiency for C2+ liquid products (30 % at -1.0 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  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.

Linking the evolution of catalytic properties and structural changes in copper-zinc nanocatalysts using operando EXAFS and neural-networks.

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.

Operando Insight into the Correlation between the Structure and Composition of CuZn Nanoparticles and Their Selectivity for the Electrochemical CO2 Reduction.

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 (∼5 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 [∼70% 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.

Electrochemical Real-Time Mass Spectrometry (EC-RTMS): Monitoring Electrochemical Reaction Products in Real Time.

Methods that provide real-time information are essential to resolve transients occurring at dynamic interfaces. Now a powerful method is presented that enables the time- and potential-resolved characterization of liquid and gaseous products of electrochemical reactions shortly after their formation. To demonstrate its extraordinary potential, the electrochemical real time mass spectrometry (EC-RTMS) approach is used to determine the products of the CO2 reduction reaction (CO2 RR) during potential step or sweep experiments on pristine and in situ anodized copper. The enhanced formation of several C2+ products over C1 products is tracked directly after copper anodization, with unprecedented temporal resolution. This new technique creates exciting new opportunities for resolving processes that occur at short timescales and eventually for guiding the design of new, robust catalysts for selective electrosynthesis under dynamic operation.