Interfacial pH Research Articles

Concurrent Regulation of Surface Topography and Interfacial Physicochemistry via Trace Chelation Acid Additives toward Durable Zn Anodes

AbstractElectrolyte additive engineering is a feasible protocol in improving Zn anode stability. Typical additive designs center on the regulation of Zn deposition; nevertheless, versatile additives are urgently requested to comprehensively manage the surface landscape, interface physicochemistry, and by‐product elimination. Here, a straightforward strategy is presented to meet such needs employing an environmentally‐friendly chelator, hydroxyethyl‐ethylenediaminetriacetate acid (HEDTA), as an additive for ZnSO4 electrolyte. Throughout theoretical computations and experimental investigations, it is demonstrated that protons released from the gradual ionization of HEDTA during rest periods aid in the mild engraving of the Zn surface. Both the amino and carboxyl groups of HEDTA⁻ can be protonated, which effectively buffers the interfacial pH value in the entire battery lifespan and eliminates the formation of by‐products. The HEDTA− anions can also adsorb onto the Zn surface, helping facilitate Zn2⁺ mass transfer and accelerate the desolvation process. Benefiting from the synchronous modulation of surface topography and interfacial physicochemistry, the assembled half cells affording HEDTA additive maintain a durable operation of up to 8821 cycles at 5.0 mA cm−2/1.0 mAh cm−2. Additionally, symmetric cells manifest stable cycling for over 4600 h at 0.5 mA cm−2/0.25 mAh cm−2.

Multifunctional Amphoteric Additive Alanine Enables High-Performance Wide-pH Zn Metal Anodes.

Interfacial pH fluctuation is one of the primary reasons for issues related to Zn metal anodes. Herein, polar amphoteric alanine, as a multifunctional electrolyte additive, is designed to regulate the electric double layer (EDL) and solvation structure. Alanine with self-adaptation capability to pH can stabilize electrolyte pH. Due to more negative adsorption energy, alanine preferentially adsorbs on the Zn surface and repels water molecules within the EDL. Alanine-enriched EDL effectively shields the surface tips, homogenizes interfacial electric field distribution, and promotes preferential deposition of horizontal flaky Zn. Alanine-enriched EDL limits the contact between water and the Zn anode. Alanine additive decreases the quantity of water molecules in the Zn2+ solvation sheath and disrupts H-bond networks in the electrolyte. Consequently, a dense and textured Zn deposition is achieved. Corrosion and side reactions are suppressed. Cycling stability of symmetrical cells attains 2700h at 3mAcm-2/1mAhcm-2 and 2050h at 5mAcm-2/1mAhcm-2. Average coulombic efficiency reaches 99.8% over 4500 cycles at 5mAcm-2/1mAhcm-2. Even within KOH alkaline electrolytes, alanine additive still improves the cycling lifespan of symmetrical cells to 100h at 0.5mAcm-2/0.5mAhcm-2.

Synergistic Cationic Shielding and Anionic Chemistry of Potassium Hydrogen Phthalate for Ultrastable Zn─I2 Full Batteries.

Electrolyte additives are investigated to resolve dendrite growth, hydrogen evolution reaction, and corrosion of Zn metal. In particular, the electrostatic shielding cationic strategy is considered an effective method to regulate deposition morphology. However, it is very difficult for such a simple cationic modification to avoid competitive hydrogen evolution reactions, corrosion, and interfacial pH fluctuations. Herein, multifunctional additives of potassium hydrogen phthalate (KHP) based on the synergistic design of cationic shielding and anionic chemistry for ultrastable Zn||I2 full batteries are demonstrated. K cations, acting as electrostatic shielding cations, constructed the smooth deposition morphology. HP anions can enter the first solvation shell of Zn2+ for the reduced activities of H2O, while they remain in the primary solvation shell and are finally involved in the formation of SEI, thus accelerating the charge transfer kinetics. Furthermore, by in situ monitoring the near-surface pH of the Zn electrode, the KHP additives can effectively inhibit the accumulation of OH- and the formation of by-products. Consequently, the symmetric cells achieve a high stripping-plating reversibility of over 4500 and 2600 h at 1.0 and 5mA cm-2, respectively. The Zn||I2 full cells deliver an ultralong term stability of over 1400 cycles with a high-capacity retention of 78.5%.

The Multifaceted Role of Boric Acid in Nickel Electrodeposition and Electroforming

This study involved an investigation of the role of boric acid in nickel electroforming from sulfamate electrolytes, especially in relation to its ability to minimise interfacial pH changes during electrodeposition. Initial speciation calculations indicated that buffering by polyborate species and nickel-borate complexes are most likely responsible for this effect. However, the concentration of nickel-borate complexes was too low even at elevated pH to be a significant electroactive species. Polarisation and electrochemical quartz crystal microbalance measurements indicated that, in the absence of boric acid, electrodeposits typically contained Ni(OH)2, while boric acid additions resulted in pure Ni being deposited with a current efficiency approaching unity. Boric acid additions substantially modified the nickel and hydrogen partial currents, and influenced the overall current efficiency. Studies in nickel-free solutions indicated that boric acid adsorbs on the surface which explains the suppression of H2O reduction observed in the electroforming experiments. Collectively, solution buffering due to polyborate and nickel-borate species and inhibition of H2O reduction by adsorbed boric acid minimised interfacial pH changes and prevented the formation of nickel hydroxide.

Pyrrolic‐Nitrogen Chemistry in 1‐(2‐hydroxyethyl)imidazole Electrolyte Additives toward a 50,000‐Cycle‐Life Aqueous Zinc‐Iodine Battery

Rechargeable aqueous zinc iodine (Zn‐I2) batteries offer benefits such as low cost and high safety. Nevertheless, their commercial application is hindered by hydrogen evolution reaction (HER) and polyiodide shuttle, which result in a short lifespan. In this study, 1‐(2‐hydroxyethyl)imidazole (HEI) organic molecules featuring pyrrole‐N groups are introduced as dually‐functional electrolyte additives to simultaneously stabilize Zn anode and confine polyiodide through ion‐dipole interactions. The pyrrole‐N groups in HEI can preserve the interfacial pH equilibrium at Zn anode by reversibly capturing H+ ions and dynamically neutralizing OH− ions, thereby suppressing the HER. Notably, the H2 evolution rate at the Zn anode is reduced to a mere 2.20 µmol h−1 cm−2. Furthermore, the pyrrole‐N moieties in HEI effectively curtail the polyiodide shuttle at I2 cathode, which show adsorption energies of −0.174 eV for I2, −0.521 eV for I3−, and −0.768 eV for I−, as indicated by density functional theory calculations. Electrochemical testing demonstrates that the Zn//Zn symmetric cell maintains stable cycling for up to 4,200 hours at 1 mA cm−2. Most strikingly, at a high I2 mass loading of 9.7 mg cm−2, the Zn‐I2 battery achieves an extraordinary cycle life of 50,000 cycles.

Pyrrolic-Nitrogen Chemistry in 1-(2-hydroxyethyl)imidazole Electrolyte Additives toward a 50,000-Cycle-Life Aqueous Zinc-Iodine Battery.

Rechargeable aqueous zinc iodine (Zn-I2) batteries offer benefits such as low cost and high safety. Nevertheless, their commercial application is hindered by hydrogen evolution reaction (HER) and polyiodide shuttle, which result in a short lifespan. In this study, 1-(2-hydroxyethyl)imidazole (HEI) organic molecules featuring pyrrole-N groups are introduced as dually-functional electrolyte additives to simultaneously stabilize Zn anode and confine polyiodide through ion-dipole interactions. The pyrrole-N groups in HEI can preserve the interfacial pH equilibrium at Zn anode by reversibly capturing H+ ions and dynamically neutralizing OH- ions, thereby suppressing the HER. Notably, the H2 evolution rate at the Zn anode is reduced to a mere 2.20 µmol h-1 cm-2. Furthermore, the pyrrole-N moieties in HEI effectively curtail the polyiodide shuttle at I2 cathode, which show adsorption energies of -0.174 eV for I2, -0.521 eV for I3-, and -0.768 eV for I-, as indicated by density functional theory calculations. Electrochemical testing demonstrates that the Zn//Zn symmetric cell maintains stable cycling for up to 4,200 hours at 1 mA cm-2. Most strikingly, at a high I2 mass loading of 9.7 mg cm-2, the Zn-I2 battery achieves an extraordinary cycle life of 50,000 cycles.

(Invited) Probing the Reaction Microenvironment during Electrochemical Nitrate Reduction to Ammonia

Nitrate pollution of wastewater from agricultural runoff and industrial waste streams is common around the globe. Nitrate negatively impacts the environment through harmful algal blooms and can be dangerous for human consumption. Strict limits have been set on nitrate discharge and the concentration in drinking water (< 50 ppm). Nitrate is currently removed from water by conversion to nitrogen through a biological process that requires chemical inputs (e.g., methanol) and post-treatment to remove biomass and organics.Electrochemical reduction of nitrate (NO3RR) to ammonia can remove nitrate from water and is an alternative to Haber-Bosch (HB) ammonia production, a significant source of global CO2 emissions. Ammonia is an important chemical precursor with potential applications in sustainable energy as a fuel or H2 carrier, or can be used as a fertilizer in the form of ammonium sulfate. This research addresses the water–energy nexus by converting nitrate to a valuable product, off-setting the cost of water treatment, and reducing demand for HB.NO3RR can be done from small to large scales, use renewable electricity, and eliminate the need for expensive and hazardous chemicals. However, NO3RR processes must exhibit selectivity toward ammonia to avoid the formation of other undesired products and occur at a low overpotential to minimize operating costs from electricity. To address these challenges, we must understand the reaction environment at the electrode–electrolyte interface, where heterogeneous electrochemical reactions occur. We use in situ attenuated total reflectance–surface-enhanced infrared adsorption spectroscopy (ATR–SEIRAS) to investigate the adsorbed reactants, intermediates, and interfacial pH. We studied the repeatability of the technique for in situ interfacial pH measurement and recommend controls to the community when using this method. The ATR–SEIRAS results are correlated with electrochemical experiments measuring NO3RR selectivity, activity, and efficiency. NO3RR products are measured by ion chromatography and gas chromatography. Our results relate bulk electrolyte properties with interfacial properties, and interfacial properties with reaction activity and selectivity. This understanding could lead to the development of electrolyte engineering strategies to optimize ammonia production in electrochemical NO3RR.

The role of cations in hydrogen evolution reaction on a platinum electrode in mildly acidic media

In this work, we study the influence of cation concentration and identity on the hydrogen evolution reaction (HER) on polycrystalline platinum (Pt) electrode in pH 3 electrolytes. Our observations indicate that cations in the electrolyte do not affect proton reduction at low potentials. However, an increase in cation concentration significantly enhances water reduction. Simultaneously, we identify a non-negligible migration current under mass transport limited conditions in electrolytes with low cation concentration. To separate migration effects from specific cation-promotion effects on HER, we carried out further experiments with electrolytes with mixtures of Li+ and K+ cations. Our results show that, adding strongly hydrated cations (Li+) to a K+-containing electrolyte leads to a less negative onset potential of water reduction. Interfacial pH measurements reveal a same interfacial pH at the platinum electrode in pH 3 in the presence of 80 mM LiClO4 and KClO4, respectively, at potentials where water reduction occurs. Based on these results, we suggest that under the current conditions, the strongly hydrated cations (Li+) promote water dissociation on the Pt electrode more favorably in comparison with the more weakly hydrated cations (K+), and that this promotion is not related to a local pH effect.

In Situ Assembly of Metal‐Organic Coordination Polymer Layers Enables Highly Reversible Zn Anodes with a Long Cycle Life of over 6900 h

AbstractZn anodes in aqueous zinc‐ion batteries chronically suffer from pernicious side reactions and ineluctable dendrite growth, resulting in inadequate reversibility and suboptimal Coulombic efficiency (CE) and impeding commercialization. Herein, a multifunctional metal–organic coordination polymer layer (FAZ) is constructed on the zinc anode surface (FAZ@Zn) utilizing a simple self‐assembly strategy. The zincophilic FAZ interfacial layer with a high Zn2+ transfer number and low nucleation barrier effectively facilitates the de‐solvation process, supports the rapid transport of zinc ions, and contributes to the preferential growth of Zn (002) crystal planes, enabling dendrite‐free Zn deposition. Furthermore, the FAZ layer, as an interfacial pH regulating layer, effectively inhibits the direct contact between Zn and active water molecules, lowering the severity of side reactions. Consequently, the FAZ@Zn anode furnishes an eminent cycle stability over 6900 h, with a low polarization voltage at 1 mA cm−2 and 1 mA h cm−2 and a boosted CE of 99.88% over 4100 cycles. More encouragingly, when coupled with Na2V6O16·3H2O, the FAZ@Zn anode enables the full cell to deliver satisfactory rate performance and a 97% capacity retention over 1600 cycles. This work provides a simple strategy for the effective preparation of highly reversible zinc anodes for high‐performance aqueous zinc‐ion batteries.

Suppressing Competing Solvent Reduction in CO2 Electroreduction with a Magnetic Field.

The presence of an external magnetic field is found to affect the competition between the H2O and CO2 reduction reactions by increasing mass transport via the Lorentz force. Increasing the magnetic field strength at the electrode surface from 0 to 325 mT increases the selectivity of CO over H2 by 3×, while an increase in current density from 0.5 to 5 mA/cm2 increases the selectivity of CO production by 5×. Cyclic voltammetry and finite-element simulations reveal that the origin of the enhanced CO selectivity is attributable to a magnetic field lowering the electrode-electrolyte interfacial pH. A drop in interfacial pH enables increased production of CO from CO2 reduction due to a decrease in the activity of H2O reduction and increase in CO2 solubility near the electrode surface. The insight provided in this study offers new opportunities to control reaction selectivity in electrocatalysis with magnetic field vectors.

The Influence of Alkali Cations on the Performance of Pt Electrodes in Kolbe Electrolysis of Acetic Acid

AbstractElectrochemical decarboxylation of carboxylic acids is considered a sustainable method to improve the quality of pyrolysis oil. In this study, we assess the effect of monovalent alkali cations (of the acetates) on the performance of Pt electrodes in acid decarboxylation and the competing OER, using various electrochemical methods. We reveal a strong cation dependence generally following the trend Li+&lt;Na+&lt;K+~Cs+ within a large pH range. Using rotating ring disc electrode measurements, we highlight the strong contribution of the oxygen evolution reaction particularly for electrolytes containing Li+ and Na+ which decreases the selectivity for Kolbe oxidation. In addition, the faradaic efficiency (FE) towards methanol ranges between 16 % (for Li+) and 29 % (for Cs+) at high solution pH (9 or 12). The observed trends are generally explained by a cation‐dependent interfacial pH and surface coverage of acetate, both lowest for Li. This is evident from differences in charge transfer resistance determined by impedance measurements and local pH measurements. Additionally, enhanced dissolution of Pt by Li+ is also proposed. This work highlights that K+ and Cs+ cations favor FE for electrochemical Kolbe oxidation, at relatively low current densities.

Highly Efficient Acidic Electrosynthesis of Hydrogen Peroxide at Industrial-Level Current Densities Promoted by Alkali Metal Cations.

Acidic H2O2 synthesis through electrocatalytic 2e- oxygen reduction presents a sustainable alternative to the energy-intensive anthraquinone oxidation technology. Nevertheless, acidic H2O2 electrosynthesis suffers from low H2O2 Faradaic efficiencies primarily due to the competing reactions of 4e- oxygen reduction to H2O and hydrogen evolution in environments with high H+ concentrations. Here, we demonstrate the significant effect of alkali metal cations, acting as competing ions with H+, in promoting acidic H2O2 electrosynthesis at industrial-level currents, resulting in an effective current densities of 50-421 mA cm-2 with 84-100 % Faradaic efficiency and a production rate of 856-7842 μmol cm-2 h-1 that far exceeds the performance observed in pure acidic electrolytes or low-current electrolysis. Finite-element simulations indicate that high interfacial pH near the electrode surface formed at high currents is crucial for activating the promotional effect of K+. In situ attenuated total reflection Fourier transform infrared spectroscopy and ab initio molecular dynamics simulations reveal the central role of alkali metal cations in stabilizing the key *OOH intermediate to suppress 4e- oxygen reduction through interacting with coordinated H2O.

Highly Efficient Acidic Electrosynthesis of Hydrogen Peroxide at Industrial‐Level Current Densities Promoted by Alkali Metal Cations

AbstractAcidic H2O2 synthesis through electrocatalytic 2e− oxygen reduction presents a sustainable alternative to the energy‐intensive anthraquinone oxidation technology. Nevertheless, acidic H2O2 electrosynthesis suffers from low H2O2 Faradaic efficiencies primarily due to the competing reactions of 4e− oxygen reduction to H2O and hydrogen evolution in environments with high H+ concentrations. Here, we demonstrate the significant effect of alkali metal cations, acting as competing ions with H+, in promoting acidic H2O2 electrosynthesis at industrial‐level currents, resulting in an effective current densities of 50–421 mA cm−2 with 84–100 % Faradaic efficiency and a production rate of 856–7842 μmol cm−2 h−1 that far exceeds the performance observed in pure acidic electrolytes or low‐current electrolysis. Finite‐element simulations indicate that high interfacial pH near the electrode surface formed at high currents is crucial for activating the promotional effect of K+. In situ attenuated total reflection Fourier transform infrared spectroscopy and ab initio molecular dynamics simulations reveal the central role of alkali metal cations in stabilizing the key *OOH intermediate to suppress 4e− oxygen reduction through interacting with coordinated H2O.

Proton-driven bilateral interfacial chemistry and electrolyte structure reconstruction enable highly reversible zinc metal anodes

Uncontrolled dendrite growth, severe parasitic reactions on the Zn metal anode (ZMA), and the dissolution of cathode active materials have significantly limited the development of aqueous zinc ion batteries. Herein, 3-(Cyclohexylamino)-1-propanesulfonic acid (CAPS) featured with zwitterion as a multifunctional additive is introduced into the 2 M ZnSO4 aqueous electrolyte to simultaneously regulate the interfacial chemistry of the Zn anode and the cathode, as well as the solvated structure of Zn2+, thereby improving the interfacial and structural stability of both electrodes. Thereinto, the preferentially adsorbed CAPS zwitterion onto the ZMA surface favors for constructing a cationic protective layer originated from the electrostatic shielding effect of the cationic group (>NH2+), inhibiting the growth of dendrites. Meanwhile, the CAPS zwitterion can self-regulate the bilateral interfacial pH by forming the conjugate acid-base pair, suppressing hydrogen evolution reaction and Zn anode surface corrosion. Additionally, the CAPS zwitterion alters the solvated structure of Zn2+, weakening H2O molecule activity and reducing the dissolution of vanadium element from cathode. Consequently, the Zn||Zn symmetric cells harvest excellent cycling stability (1 mA cm−2, 1 mAh cm−2, 2300 h), and the Zn||Cu asymmetric cells display a high average Coulombic Efficiency of 99.7 % after 1600 cycles in the ZnSO4+CAPS electrolyte.

ATR-SEIRAS Method to Measure Interfacial pH during Electrocatalytic Nitrate Reduction on Cu

This study reports the accuracy and applications of an attenuated total reflectance–surface-enhanced infrared absorption spectroscopy (ATR–SEIRAS) technique to indirectly measure the interfacial pH of the electrolyte within 10 nm of the electrocatalyst surface. This technique can be used in situ to study aqueous electrochemical reactions with a calibration range from pH 1–13, time resolution down to 4 s, and an average 95% confidence interval of 14% that varies depending on the pH region (acidic, neutral, or basic). The method is applied here to electrochemical nitrate reduction at a copper cathode to demonstrate its capabilities, but is broadly applicable to any aqueous electrochemical reaction (such as hydrogen evolution, carbon dioxide reduction, or oxygen evolution) and the electrocatalyst may be any SEIRAS-active thin film (e.g., silver, gold, or copper). The time-resolved results show a dramatic increase in the interfacial pH from pH 2–7 in the first minute of operation during both constant current and pulsed current experiments where the bulk pH is unchanged. Attempts to control the pH polarization at the surface by altering the electrochemical operating conditions—lowering the current or increasing the pulse frequency—showed no significant change, demonstrating the challenge of controlling the interfacial pH.

Manipulating Interfacial pH by the Base-Catalyzed Hydrolysis Strategy for Highly Reversible Zinc Anodes

Manipulating Interfacial pH by the Base-Catalyzed Hydrolysis Strategy for Highly Reversible Zinc Anodes

Open circuit potential decay transients quantify interfacial pH swings during high current density hydrogen electrocatalysis

Open circuit potential decay transients quantify interfacial pH swings during high current density hydrogen electrocatalysis

Electrochemical silica removal from carbon nanotube surfaces: Energy consumption and removal mechanisms

Inorganic fouling, or scaling, is a major challenge for engineered systems exposed to aqueous environments, particularly in water treatment, desalination, or thermal systems where the high salinity and temperature conditions favor surface scaling. Silica, in particular, is hard to remove once a scaling layer forms on the surface. Current scaling mitigation strategies include the addition of antiscalants, physical cleaning by flushing or backwashing, and pretreatment of the feed water. These mitigation strategies increase operation costs due to increased chemical use and system downtime, as well increase the complexity of the process. In this work, we investigated the ability of carbon nanotube (CNT) coatings to disperse silica from the surface via electrochemical reactions, providing a chemical-free approach to scaling control. Silica scaling was induced and then dispersed from CNT coupons upon the application of a potential difference across the experimental set up, with the CNT coupon acting as a cathode or anode. Scale removal was measured using optical coherence tomography at different applied current densities. In this study, a cathodic current of 2.5 A/m2 was found to achieve the highest silica removal: > 75% after 30 min. Control experiments conducted using pH-buffered solutions and pH-insensitive gypsum as the scaling mineral suggest that silica dispersion from the CNT surface was due to a combination of gas evolution and interfacial pH change. These results provide a better understanding of the potential of using electrochemical coatings for the removal of inorganic fouling from surfaces.

Determination of divalent metal ion-regulated proton concentration and polarity at the interface of anionic phospholipid membranes.

We studied the influence of trace quantities of divalent metal ions (M2+: Ca2+, Mg2+, and Zn2+) on proton concentration (-log[H+], designated as pH') and polarity at the interface of anionic PG-phospholipid membranes comprising saturated and unsaturated acrylic chains. A spiro-rhodamine-6G-gallic acid (RGG) pH-probe was synthesized to monitor the interfacial pH' of large unilamellar vesicles (LUVs) at a physiologically appropriate bulk pH (6.0-7.5). 1H-NMR spectroscopy and fluorescence microscopy showed that RGG interacted with the LUV interface. The pH-dependent equilibrium between the spiro-closed and spiro-open forms of RGG at the interface from the bulk phase was compared using fluorescence spectra to obtain interfacial pH'. Interfacial dielectric constant (κ) was estimated using a porphyrin-based polarity-probe (GPP) that exhibits a κ-induced equilibrium between monomeric and oligomeric forms. M2+ interaction decreased LUV interfacial κ from ∼67 to 61, regardless of lipid/M2+ types. Fluorescence spectral and microscopic analysis revealed that low Ca2+ and Mg2+ amounts (M2+/lipid = 1 : 20 for unsaturated DOPG and POPG and ∼1 : 10 for saturated DMPG lipids), but not Zn2+, decreased LUV interfacial acidity from pH' ∼3.8 to 4.4 at bulk pH 7.0. Although membrane surface charges are normally responsible for pH' deviation from the bulk to the interface, they cannot explain M2+-mediated interfacial pH' increase since there is little change in surface charges up to a low M2+/lipid ratio of <1/10. M2+-induced tight lipid headgroup packing and the resulting increased surface rigidity inhibit interfacial H+/H2O penetration, reducing interfacial acidity and polarity. Our findings revealed that in certain cases, essential M2+ ion-induced bio-membrane reactivity can be attributed to the influence of interfacial pH'/polarity.

The Influence of the Interfacial pH on the Electrochemical CO2 Reduction Towards Formate on Cu Electrodes

The electrochemical reduction of CO2 (CO2RR) using renewable electricity is considered a promising way to replace fossil fuels as feedstock. In aqueous media, the activity and selectivity for the CO2RR is strongly influenced by electrolyte composition at the solid-electrolyte interface. Due to competing H+ reduction, the interfacial pH is strongly affected by the applied potential which in turn determines the balance between CO2, HCO3 -, and CO3 2-. The Bicarbonate equilibrium and cation-hydroxide interactions are directly connected to the CO2RR and HER rate.[1]To learn more about the impact of the electrolyte composition within the double layer on the CO2RR mechanism we deploy time-resolved (sub-second) FT-IR reflection-absorption spectro-electrochemistry at grazing angle using polarized light. This allows us to differentiate conversions at the electrode-electrolyte interface (i.e. CO2RR) from the diffuse double layer (i.e. pH effects). Herein, we elucidate the electrochemical CO2RR towards formate on polycrystalline Cu in aqueous bicarbonate electrolyte. We compare the rate of CH formation to the interfacial pH changes determined by the ratio between the intensity of the CO2, HCO3 -, and CO3 2- bands. We discuss how potential steps and sweeps relate to interfacial pH and CO2RR.By applying a ‘pre’potential more positive from the open circuit potential (OCP: ca. +0.5 V vs. RHE) before stepping to -0.9 V vs. RHE, the interfacial pH decreases due to the oxidation of Cu. As a result, the rate of C-H formation is initially hindered for several seconds before setting off. Likewise, an applied ‘pre’potential more negative from the OCP results into poor C-H formation kinetics.Reference:[1] Liu, X.; Monteiro, M.C.O.; Koper, M. T. M. Phys. Chem. Chem. Phys. 2023, advance article. Figure 1