Attenuated Total Reflection Surface Enhanced Infrared Absorption Spectroscopy Research Articles

Key Structure Parameters for Designing High-Performance Substrates of Surface-Enhanced Infrared Absorption Spectroelectrochemistry.

Attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) plays a crucial role in understanding the interfacial reaction mechanisms at the molecular level, achieving an enhancement factor (EF) of up to 103. However, when this technique is integrated with electrochemistry (EC-ATR-SEIRAS), the EF is significantly reduced by ten- to hundred-fold. Thus, understanding of the key parameters that contribute to the EF is of great importance in designing high-performance substrates and extending the application for EC-SEIRAS. In this study, we propose that the structure of the substrate for EC-ATR-SEIRAS consists of an enhancement unit (EU) supported on a conductivity unit (CU). The CU will screen the incident IR light reaching and interacting with the EU, resulting in a smaller EF as the CU thickness increases. Then, we introduce a strategy to optimize the performance of the EC-SEIRAS substrate by assembling a plasmonic antenna array as the EU that is supported on IR-transparent and conductive monolayer graphene as the CU. The established plasmon-enhanced EC-SEIRAS substrate demonstrates much higher IR enhancement, repeatability, and stability.

Atomically precise (AgPd)27 nanoclusters for nitrate electroreduction to NH3: Modulating the metal core by a ligand induced strategy

Electrochemical nitrate reduction reaction (eNO3–RR) to synthesize NH3 is a sustainable method to convert environmental contaminants into valuables. Pd based bimetallic nanocatalysts have demonstrated great promise as efficient catalysts, yet modulating the composition and configuration to improve the catalytic performance and achieve comprehensive mechanistic understanding remains challenging. Herein, by employing two ligands with different electron functional groups, we successfully prepared two atomically precise (AgPd)27 bimetallic clusters of Ag18Pd9(C8H4F)24 (Ag18Pd9) and Ag22Pd5(C9H10O2)26 (Ag22Pd5). The two clusters possess markedly different metal core composition and configuration, where Ag18Pd9 has a sandwich metal core structure with 9 Pd atoms located in the middle layer and Ag22Pd5 has a rod-shaped metal core structure composed of the M13 configuration with 5 Pd atoms located at the center and vertices of the M13 configuration. Unexpectedly, Ag22Pd5 exhibited remarkably superior eNO−3RR performance than Ag18Pd9. Specifically, the highest Faradaic efficiency of NH3 (FENH3) and its yield rate can reach 94.42 ​% and 1.41 ​mmol ​h−1 ​mg−1 ​at −0.6 ​V vs. RHE for Ag22Pd5, but the largest FENH3 and NH3 yield rate is only 43.86 ​% and 0.41 ​mmol ​h−1 ​mg−1 ​at −0.5 ​V vs. RHE for Ag18Pd9. The in situ attenuated total reflection surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) test provides the experimental evidence of the reaction intermediates hence revealing the reaction pathway, also shows that Ag22Pd5 has stronger capability for NO−3 adsorption and NH3 desorption than that of Ag18Pd9. Theoretical calculations indicate that the de-ligated clusters can expose the available AgPd bimetallic sites, synergistically serving as effective active sites and the different configurations result in significantly different catalytic activities, where the active sites in Ag22Pd5 are more favorable for NO−3 adsorption and NH3 desorption to accelerate the catalytic process.

In Situ Surface-Enhanced Infrared Absorption Spectroscopy to Explore the Stability of Electrolyte in Nonaqueous Lithium Oxygen Batteries

Tetraethylene glycol dimethyl ether (TEGDME) decomposition on the Au electrode surface is studied using in situ attenuated total reflectance surface enhanced infrared absorption spectroscopy (ATR-SEIRAS). Due to the weak solvation of TEGDME, the superoxide intermediate (LiO2/O2−) of the discharge process rapidly gains electrons on the electrode surface to generate Li2O2. Furthermore, alkyl radical, formed by LiO2/O2− extracting hydrogen from ether, undergoes oxidative decomposition reactions to form by-products. During the charge process, amorphous film-like Li2O2 obtained from surface-phase mechanism oxidizes in the low potential range of 3–3.4 V, while the oxidation potential of large-sized crystal Li2O2 particles obtained from solution-phase mechanism is above 3.4 V. Besides, TEGDME is intrinsically unstable and can decompose at 3.8 V even the solution is saturated with argon, indicating that the degradation of ether-based electrolyte is inevitable during the cycling process. This work confirms the feasibility of ATR-SEIRAS in probing the reaction mechanism and electrolyte stability of lithium oxygen batteries, and provides direct spectroscopic evidence for subsequent optimization of electrolyte components.

(Invited) Operando Spectroscopic Analysis for Understanding Interfacial Photo/Electrocatalytic Processes

Observing key intermediates directly on the catalyst surface poses a significant challenge in various photo/electrocatalytic processes, including CO2 reduction and O2 reduction reactions. To gain a comprehensive understanding of the reaction mechanisms, it is essential to conduct combined studies utilizing complementary tools such as electrochemical characterization, computational calculations, and operando spectroscopies. Among these, time-resolved attenuated total reflection-surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) stands out as particularly suited for investigating electrochemical CO2RR due to its ability to observe interfacial processes in real-time with high surface sensitivity. Time-resolved analysis offered by ATR-SEIRAS allows for the exploration of the kinetic relevance of intermediates and their dynamics in relation to reactants and products during the reaction. Furthermore, integrating operando spectroscopic studies with material characterization enables the correlation of intermediate behavior with catalyst conditions. In this context, I will introduce in situ time-resolved FT-IR (or ATR mode) spectroscopic techniques to capture isotopically labeled products and key intermediates generated during the photoreduction of carbon dioxide.

Exploring the Impact of Excess Cations in Acidic CO2 Reduction Reaction

To anticipate high performance in the electrocatalytic reactions, a comprehensive understanding of the electric double layer (EDL) is essential. Experimental, spectroscopic, and computational studies of the EDL have been reported for understanding the performance in electrocatalytic reactions such as the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and CO2 reduction reaction (CO2RR). Notably, in the CO2RR, previous studies have revealed the accumulation of cations near the outer Helmholtz plane (OHP) significantly has an impact on the reaction performance, product selectivity, and partial current density. The presence of these cations induces various effects, such as creating a strong electric field, altering local pH levels, stabilizing the intermediates, and specific adsorption. However, unraveling the sole cation effect remains challenging due to the system's complexity and hierarchical characteristics. Moreover, experiments predominantly conducted under favorable conditions for understanding the electric field and stabilization effects have left the specific adsorption effect relatively unexplored. Specific adsorption involves direct coordination with the electrode at the inner Helmholtz plane (IHP), with the degree determined by catalyst type and electrolyte conditions. Previous studies have highlighted the significant impact of specific adsorption on current density and intermediate stabilization, with potassium (K+) and cesium (Cs+) cation exhibiting the most pronounced effect owing to their minimal hydration degree compared to the lithium (Li+) and sodium (Na+).Acidic CO2RR has recently garnered attention for its high carbon efficiency (CE) and energy efficiency (EE). However, the abundance of hydronium ions can lead to a favorable occurrence of HER over CO2RR due to its facile protonation. To mitigate this challenge, excess cations have been employed to suppress the hydronium ion migration and enhance the performance of the CO2RR, which means accumulated cation layer at the OHP can suppress the HER and stabilize the intermediates of the CO2RR simultaneously. Meanwhile, in the excess cation condition, adsorbed cations can be dominant on the electrode originated from the excess cations, which is not investigated intensively. For the better performance of the electrocatalytic reactions in the acidic condition, we need to elucidate the EDL formed in the presence of the excess cations.In here, we investigated the electrode-electrolyte interface in the different cation species during the acidic CO2RR through the attenuated total reflection-surface enhanced infrared absorption spectroscopy (ATR-SEIRAS), which can give the local information such as the adsorbed species on the metal and free species near the electrode. We confirmed the different product distribution and interface depending on the cation species, especially in the excess cations (1 M M+, M = Li, K, Cs). Specific adsorption in the presence of the excess cations can alter the product distribution, and it differs from the low cation concentration (0.1 M M+, M = Li, K, Cs). In final, to clarify the effect originated from the excess cations, we confirmed the interface on the copper and silver, which major products are C2+ and C1, respectively.

Hydrogen Spillover-Bridged Interfacial Water Activation of WCx and Hydrogen Recombination of Ru as Dual Active Sites for Accelerating Electrocatalytic Hydrogen Evolution.

Tungsten carbide (WCx) is a promising alternative to platinum catalysts for hydrogen evolution reaction (HER). However, strong tungsten-hydrogen bond hinders hydrogen desorption while favoring H+ reduction, thus limiting HER kinetics. Inspired by the phenomenon of hydrogen spillover in heterogeneous catalysis, a ruthenium (Ru) doped-driven activated hydrogen migration from WCx surface to Ru is reported. This approach achieved high activity with an ultralow overpotential of 9.0mV at 10 mA·cm-2 and superior stability at an industrial-grade current density of 1.0 A·cm-2 @ 1.65V. In situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS)and operando electrochemical impedance spectra revealed that this exceptional hydrogen production-which surpasses that of previously reported Pt/C catalysts-is attributable to the outstanding ability of WCx to induce water dissociation and hydrogen spillover from WCx to Ru surface. During the HER process, the rigid interfacial water network negatively affected the HER efficiency under alkaline conditions. The WCx sites disrupted this rigid structure, facilitating the contact between activated hydrogen (H*) and WCx sites. Subsequently, H* migrates to Ru surface, where hydrogen recombination occurs to produce H2. This work paves a new avenue for the construction of coupled catalysts at the atomic scale to facilitate HER electrocatalysis.

Covalent Organic Framework Stabilized Single CoN4Cl2 Site Boosts Photocatalytic CO2 Reduction into Tunable Syngas.

Solar carbon dioxide (CO2) reduction provides an attractive alternative to producing sustainable chemicals and fuel. However, the construction of a highly active photocatalyst was challenging because of the rapid charge recombination and sluggish surface CO2 reduction. Herein, a unique Co-N4Cl2 single site was fabricated by loading Co species into the 2,2'-bipyridine and triazine-containing covalent organic framework (COF) for CO2 conversion into syngas under visible light irradiation. The resulting champion catalyst TPy-COF-Co enabled a record-high CO production rate of 426 mmol g-1 h-1, associated with the unprecedented turnover number (TON) and turnover frequency (TOF) of 2095 and 1607 h-1, respectively. The catalyst also exhibited favorable recycling performance and widely adjustable syngas production (CO/H2 ratio: 1.8 : 1-1 : 16). A systematical investigation including operando synchrotron X-ray absorption fine structure (XAFS) spectroscopy, in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS), and theoretical calculation indicated that the triazine-based COF framework promoted the charge transfer towards the single Co-N4Cl2 sites that greatly promoted the CO2 activation by lowering the energy barrier of *COOH generation, facilitating the CO2 transformation. This work highlights the great potential of the molecular regulation of COF-derived single-atom catalysts to boost CO2 photoreduction efficiency.

Covalent Organic Framework Stabilized Single CoN4Cl2 Site Boosts Photocatalytic CO2 Reduction into Tunable Syngas

AbstractSolar carbon dioxide (CO2) reduction provides an attractive alternative to producing sustainable chemicals and fuel. However, the construction of a highly active photocatalyst was challenging because of the rapid charge recombination and sluggish surface CO2 reduction. Herein, a unique Co−N4Cl2 single site was fabricated by loading Co species into the 2,2′‐bipyridine and triazine‐containing covalent organic framework (COF) for CO2 conversion into syngas under visible light irradiation. The resulting champion catalyst TPy‐COF‐Co enabled a record‐high CO production rate of 426 mmol g−1 h−1, associated with the unprecedented turnover number (TON) and turnover frequency (TOF) of 2095 and 1607 h−1, respectively. The catalyst also exhibited favorable recycling performance and widely adjustable syngas production (CO/H2 ratio: 1.8 : 1–1 : 16). A systematical investigation including operando synchrotron X‐ray absorption fine structure (XAFS) spectroscopy, in situ attenuated total reflection surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS), and theoretical calculation indicated that the triazine‐based COF framework promoted the charge transfer towards the single Co−N4Cl2 sites that greatly promoted the CO2 activation by lowering the energy barrier of *COOH generation, facilitating the CO2 transformation. This work highlights the great potential of the molecular regulation of COF‐derived single‐atom catalysts to boost CO2 photoreduction efficiency.

Enhanced CO2 Electroreduction to ethylene on Cu nanocube coated with nitrogen-doped carbon shell in-situ electro-derived from metal-organic framework

Electrochemical CO2 reduction reaction (CO2RR) to ethylene is one of the most promising technologies to achieve efficient use of carbon resources and sustainable development, in which the development of an efficient and stable electrocatalyst is particularly important. In this work, we develop a catalyst in situ electro-derived from Cu-based MOF for CO2RR to ethylene. We prepared nano Cu-MOF by microwave synthesis and supported it on a Cu foil substrate as a working electrode (denoted as MOF/Cu foil). During in situ electrolysis, Cu-MOF was converted into a highly dispersed nitrogen-doped carbon-coated Cu nanocube (denoted as Cu-cube/CN), which inhibited particle agglomeration and enhanced active site exposure. At a potential of −1.15 V vs. RHE, the Faradaic efficiency (FE) of the Cu-cube/CN catalyst for ethylene is 49.6 %, significantly higher than that of the original Cu foil electrode and Cu-MOF supported on the gas diffusion layer (GDL) prepared working electrode (denoted as MOF/GDL). In situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and density functional theory (DFT) calculations studies indicate that due to the electron-donating ability of the CN coating, the adsorption of *CO is enhanced, increasing the *CO coverage, lowering the reaction free energy of *CO dimerization, promoting C-C coupling and ethylene generation. This work provides new insights for the development of efficient and stable electrocatalysts for CO2RR-to-ethylene production.

Heterometallic Transition Metal Oxides Containing Lewis Acids as Molecular Catalysts for the Reduction of Carbon Dioxide to Carbon Monoxide with Bimodal Activity.

Electrocatalytic CO2 reduction (e-CO2RR) to CO is replete with challenges including the need to carry out e-CO2RR at low overpotentials. Previously, a tricopper-substituted polyoxometalate was shown to reduce CO2 to CO with a very high faradaic efficiency albeit at -2.5 V versus Fc/Fc+. It is now demonstrated that introducing a nonredox metal Lewis acid, preferably GaIII, as a binding site for CO2 in the first coordination sphere of the polyoxometalate, forming heterometallic polyoxometalates, e.g., [SiCuIIFeIIIGaIII(H2O)3W9O37]8-, leads to bimodal activity optimal both at -2.5 and -1.5 V versus Fc/Fc+; reactivity at -1.5 V being at an overpotential of ∼150 mV. These results were observed by cyclic voltammetry and quantitative controlled potential electrolysis where high faradaic efficiency and chemoselectivity were obtained at -2.5 and -1.5 V. A reaction with 13CO2 revealed that CO2 disproportionation did not occur at -1.5 V. EPR spectroscopy showed reduction, first of CuII to CuI and FeIII to FeII and then reduction of a tungsten atom (WVI to WV) in the polyoxometalate framework. IR spectroscopy showed that CO2 binds to [SiCuIIFeIIIGaIII(H2O)3W9O37]8- before reduction. In situ electrochemical attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) with pulsed potential modulated excitation revealed different observable intermediate species at -2.5 and -1.5 V. DFT calculations explained the CV, the formation of possible activated CO2 species at both -2.5 and -1.5 V through series of electron transfer, proton-coupled electron transfer, protonation and CO2 binding steps, the active site for reduction, and the role of protons in facilitating the reactions.

Electrochemical CO2 Reduction in Acidic Electrolytes: Spectroscopic Evidence for Local pH Gradients.

Inspired by recent advances in electrochemical CO2 reduction (CO2R) under acidic conditions, herein we leverage in situ spectroscopy to inform the optimization of CO2R at low pH. Using attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and fluorescent confocal laser scanning microscopy, we investigate the role that alkali cations (M+) play on electrochemical CO2R. This study hence provides important information related to the local electrode surface pH under bulk acidic conditions for CO2R, both in the presence and absence of an organic film layer, at variable [M+]. We show that in an acidic electrolyte, an appropriate current density can enable CO2R in the absence of metal cations. In situ local pH measurements suggest the local [H+] must be sufficiently depleted to promote H2O reduction as the competing reaction with CO2R. Incrementally incorporating [K+] leads to increases in the local pH that promotes CO2R but only at proton consumption rates sufficient to drive the pH up dramatically. Stark tuning measurements and analysis of surface water structure reveal no change in the electric field with [M+] and a desorption of interfacial water, indicating that improved CO2R performance is driven by suppression of H+ mass transport and modification of the interfacial solvation structure. In situ pH measurements confirm increasing local pH, and therefore decreased local [CO2], with [M+], motivating alternate means of modulating proton transport. We show that an organic film formed via in situ electrodeposition of an organic additive provides a means to achieve selective CO2R (FECO2R ∼ 65%) over hydrogen evolution reaction in the presence of strong acid (pH 1) and low cation concentrations (≤0.1 M) at both low and high current densities.

Sulfur-Bridged Asymmetric CuNi Bimetallic Atom Sites for CO2 Reduction with High Efficiency.

Double-atom catalysts (DACs) with asymmetric coordination are crucial for enhancing the benefits of electrochemical carbon dioxide reduction and advancing sustainable development, however, the rational design of DACs is still challenging. Herein, this work synthesizes atomically dispersed catalysts with novel sulfur-bridged Cu-S-Ni sites (named Cu-S-Ni/SNC), utilizing biomass wool keratin as precursor. The plentiful disulfide bonds in wool keratin overcome the limitations of traditional gas-phase S ligand etching process and enable the one-step formation of S-bridged sites. X-ray absorption spectroscopy (XAS) confirms the existence of bimetallic sites with N2Cu-S-NiN2 moiety. In H-cell, Cu-S-Ni/SNC shows high CO Faraday efficiency of 98.1% at -0.65V versus RHE. Benefiting from the charge tuning effect between the metal site and bridged sulfur atoms, a large current density of 550mAcm-2 can be achieved at -1.00V in flow cell. Additionally, in situ XAS, attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS), and density functional theory (DFT) calculations show Cu as the main adsorption site is dual-regulated by Ni and S atoms, which enhances CO2 activation and accelerates the formation of *COOH intermediates. This kind of asymmetric bimetallic atom catalysts may open new pathways for precision preparation and performance regulation of atomic materials toward energy applications.

Uncovering the Dissociative Adsorption of the Leveler Janus Green B on Cu Electrodes at the Molecular Level.

The interfacial adsorption structure of an organic leveler decides its functionality in Cu interconnect electroplating and is yet far from clear. In this work, in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and electrochemical quartz crystal microbalance (EQCM) in conjunction with density functional theory (DFT) calculations are applied to unravel the interfacial adsorption of the classic dye leveler Janus Green B (JGB) at a Cu electrode and understand its polarization property against Cu electrodeposition from an adsorption structure perspective. ATR-SEIRAS measurements and DFT calculations reveal that the N=N bond of the JGB molecule splits via reductive hydrogenation, forming two fragments of contrasting adsorption configurations. JGB exhibits the strongest inhibition effect on Cu deposition among all the tested additives including individual and mixed fragments, due to the highest coverage of organic adsorbates from JGB dissociation, as measured by EQCM. This work highlights the advantage of surface sensitive analytical tools in understanding the structure-performance of levelers.

Electrochemical Synthesis of Urea: Co-Reduction of Nitrite and Carbon Dioxide on Binuclear Cobalt Phthalocyanine.

Exploration of molecular catalysts with the atomic-level tunability of molecular structures offers promising avenues for developing high-performance catalysts for the electrochemical co-reduction reaction of carbon dioxide (CO2) and nitrite (NO2 -) into value-added urea. In this work, a binuclear cobalt phthalocyanine (biCoPc) catalyst is prepared through chemical synthesis and applied as a C─N coupling catalyst toward urea. Achieving a remarkable Faradaic efficiency of 47.4% for urea production at -0.5V versus reversible hydrogen electrode (RHE), this biCoPc outperforms many known molecular catalysts in this specific application. Its unique planar macromolecular structure and the increased valence state of cobalt promote the adsorption of nitrogenous and carbonaceous species, a critical factor in facilitating the multi-electron C─N coupling. Combining highly sensitive in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) with density functional theory (DFT) calculations, the linear adsorbed CO (COL) and bridge adsorbed CO (COB) is captured on biCoPc catalyst during the co-reduction reaction. COB, a pivotal intermediate in the co-reduction from CO2 and nitrite to urea, is evidenced to be labile and may be attacked by nitrite, promoting urea production. This work demonstrates the importance of designing molecular catalysts for efficient co-reduction of CO2 and nitrite to urea.

A supported Ni2 dual-atoms site hollow urchin-like carbon catalyst for synergistic CO2 electroreduction

Dual-atoms catalysts (DACs), while inheriting the advantages of maximum atom utilization ratio and excellent selectivity of single-atom catalysts (SACs), can better enhance the catalytic activity through the synergy of adjacent atoms. Therefore, DACs are considered to be very potential catalysts for CO2 to CO conversion. Its catalytic activity is greatly influenced by the coordination environment and morphology. Here, hollow urchin-like NiNC catalysts (Ni-NC(HU)-x, x = 100, 50, 25, 0) were synthesized using urchin-like nickel particles as template. By adjusting the amount of additional nitrogen source, the percentage content of pyridinic-N was adjusted as well as further affecting the coordination environment. Among them, Ni-NC(HU)-50, which had the highest content of pyridinic-N, formed a dual-atoms coordination structure and had the best catalytic performance that the CO Faradaic efficiency (FECO) reached 97.2 % at −0.9 V vs. reversible hydrogen electrode (RHE) and sustained above 95 % within 50 h. In-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and density functional theory (DFT) calculations showed that Ni-NC(HU)-50 exhibited the best performance of CO2 reduction reaction (CO2RR) by lowering the *COOH formation free energy barrier and its favorable dual desorption mechanism of *COL and *COB.

Catalytic Peculiarity of Alkali Metal Cation-Free Electrode/Polyelectrolyte Interfaces Toward CO2 Reduction.

A prominent feature of modern electrochemical technologies, such as fuel cells and electrolysis, is the employing of polyelectrolytes instead of liquid electrolytes. Unlike the well-studied electrode/liquid electrolyte interfaces, however, the catalytic characteristics of electrode/polyelectrolyte interfaces remain largely unexplored, mostly due to the lack of reliable probing methods. Herein, we report a universally applicable approach to investigating electrocatalytic reactions at electrode/polyelectrolyte interfaces under normal electrochemical conditions. By coating a thin layer of anion-exchange membrane (AEM) onto the electrode surface, solutions with bulky organic cations were well separated, thus a pure electrode/polyelectrolyte interface can be established in a regular electrochemical setup and studied using in situ spectroscopies, e.g., attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS). We found that the blank Au surface was inert toward the CO2 reduction reaction (CO2RR) in the absence of alkali metal cations, whereas coating with an AEM can dramatically turn on the catalytic activity. ATR-SEIRAS revealed that the hydrogen bond network of water at the Au/AEM interface was enhanced in comparison to that on the blank Au surface, which facilitated the hydrogenation process of the CO2RR. These findings further our fundamental understanding of the catalytic behavior of electrode/polyelectrolyte interfaces and benefit the development of relevant electrochemical technologies.

Unraveling the Mechanism of Ammonia Electrooxidation by Coupled Differential Electrochemical Mass Spectrometry and Surface-Enhanced Infrared Absorption Spectroscopic Studies.

Ammonia electrooxidation has received considerable attention in recent times due to its potential application in direct ammonia fuel cells, ammonia sensors, and denitrification of wastewater. In this work, we used differential electrochemical mass spectrometry (DEMS) coupled with attenuated total reflection-surface-enhanced infrared absorption (ATR-SEIRA) spectroscopy to study adsorbed species and solution products during the electrochemical ammonia oxidation reaction (AOR) on Pt in alkaline media, and to correlate the product distribution with the surface ad-species. Hydrazine electrooxidation, hydroxylamine electrooxidation/reduction, and nitrite electroreduction on Pt have also been studied to enhance the understanding of the AOR mechanism. NH3, NH2, NH, NO, and NO2 ad-species were identified on the Pt surface with ATR-SEIRA spectroscopy, while N2, N2O, and NO were detected with DEMS as products of the AOR. N2 is formed through the coupling of two NH ad-species and then subsequent further dehydrogenation, while the dimerization of HNOad leads to the formation of N2O. The NH-NH coupling is the rate-determining step (rds) at high potentials, while the first dehydrogenation step is the rds at low potentials. These new spectroscopic results about the AOR and insights could advance the search and design of more effective AOR catalysts.

Enhanced Electrochemical CO2 Reduction to Formate over Phosphate‐Modified In: Water Activation and Active Site Tuning

AbstractElectrochemical CO2 reduction reaction (CO2RR) offers a sustainable strategy for producing fuels and chemicals. However, it suffers from sluggish CO2 activation and slow water dissociation. In this work, we construct a (P−O)δ− modified In catalyst that exhibits high activity and selectivity in electrochemical CO2 reduction to formate. A combination of in situ characterizations and kinetic analyses indicate that (P−O)δ− has a strong interaction with K+(H2O)n, which effectively accelerates water dissociation to provide protons. In situ attenuated total reflectance surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS) measurements together with density functional theory (DFT) calculations disclose that (P−O)δ− modification leads to a higher valence state of In active site, thus promoting CO2 activation and HCOO* formation, while inhibiting competitive hydrogen evolution reaction (HER). As a result, the (P−O)δ− modified oxide‐derived In catalyst exhibits excellent formate selectivity across a broad potential window with a formate Faradaic efficiency as high as 92.1 % at a partial current density of ~200 mA cm−2 and a cathodic potential of −1.2 V vs. RHE in an alkaline electrolyte.

Enhanced Electrochemical CO2 Reduction to Formate over Phosphate-Modified In: Water Activation and Active Site Tuning.

Electrochemical CO2 reduction reaction (CO2RR) offers a sustainable strategy for producing fuels and chemicals. However, it suffers from sluggish CO2 activation and slow water dissociation. In this work, we construct a (P-O)δ- modified In catalyst that exhibits high activity and selectivity in electrochemical CO2 reduction to formate. A combination of in situ characterizations and kinetic analyses indicate that (P-O)δ- has a strong interaction with K+(H2O)n, which effectively accelerates water dissociation to provide protons. In situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) measurements together with density functional theory (DFT) calculations disclose that (P-O)δ- modification leads to a higher valence state of In active site, thus promoting CO2 activation and HCOO* formation, while inhibiting competitive hydrogen evolution reaction (HER). As a result, the (P-O)δ- modified oxide-derived In catalyst exhibits excellent formate selectivity across a broad potential window with a formate Faradaic efficiency as high as 92.1 % at a partial current density of ~200 mA cm-2 and a cathodic potential of -1.2 V vs. RHE in an alkaline electrolyte.

Promoting Electrochemical CO2 Reduction to Formate via Sulfur‐Assisted Electrolysis

AbstractElectrochemical CO2 reduction reaction (CO2RR) provides a renewable approach to transform CO2 to produce chemicals and fuels. Unfortunately, it faces the challenges of sluggish CO2 activation and slow water dissociation. This study reports the modification of Bi‐based electrocatalyst by S, which leads to a remarkable enhancement in activity and selectivity during electrochemical CO2 reduction to formate. Based on comprehensive in situ examinations and kinetic evaluations, it is observed that the presence of S species over Bi catalyst can significantly enhance its interaction with K+(H2O)n, facilitating fast dissociation of water molecules to generate protons. Further in situ attenuated total reflectance surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS) and in situ Raman spectroscopy measurements reveal that S modification is able to decrease the oxidation state of Bi active site, which can effectively enhance CO2 activation and facilitate HCOO* intermediate formation while suppressing competing hydrogen evolution reaction. Consequently, the S‐modified Bi catalyst achieves impressive electrochemical CO2RR performance, reaching a formate Faradaic efficiency (FEformate) of 91.2% at a formate partial current density of ≈135 mA cm−2 and a potential of −0.8 V versus RHE in an alkaline electrolyte.