Cooperative Effect of Cations and Catalyst Structure in Tuning Alkaline Hydrogen Evolution on Pt Electrodes.

The kinetics of hydrogen evolution reaction (HER) in alkaline media, a reaction central to alkaline water electrolyzers, is not accurately captured by traditional adsorption-based activity descriptors. As a result, the exact mechanism and the main driving force for the water reduction or HER rate remain hotly debated. Here, we perform extensive kinetic measurements on the pH- and cation-dependent HER rate on Pt single-crystal electrodes in alkaline conditions. We find that cations interacting with Pt step sites control the HER activity, while they interact only weakly with Pt(111) and Pt(100) terraces and, therefore, cations do not affect HER kinetics on terrace sites. This is reflected by divergent activity trends as a function of pH as well as cation concentration on stepped Pt surfaces vs Pt surfaces that do not feature steps, such as Pt(111). We show that HER activity can be optimized by rationally tuning these step-cation interactions via selective adatom deposition at the steps and by choosing an optimal electrolyte composition. Our work shows that the catalyst and the electrolyte must be tailored in conjunction to achieve the highest possible HER activity.

Cation Effects on Hydrogen Oxidation Reaction on Pt Single-Crystal Electrodes in Alkaline Media.

The exact mechanism behind the cation-assisted hydrogen oxidation reaction (HOR) on platinum electrodes in alkaline media remains disputed. We show that the cation effects at platinum display a remarkable structure sensitivity: not only the H adsorption but also the HOR activity on (111) terrace sites are independent of the nature of cation and cation concentration. On (110) step sites, at low cation concentration and mildly alkaline media, cations promote the HOR, whereas at more alkaline pH and consequently higher near-surface cation concentrations, the HOR is inhibition by the cations. Moreover, the role of the cation on terrace-OHad is different from that on step-OHad, as can also be observed from the inhibition of the HOR current by terrace-OHad at higher potentials. These results suggest that near the onset potential, HOR mainly takes place on steps, but under diffusion-limited conditions at higher overpotential, HOR mainly takes place on terraces.

Electrolyte Effects on CO2 Electrochemical Reduction to CO.

ConspectusThe electrochemical reduction of CO2 (CO2RR) constitutes an alternative to fossil fuel-based technologies for the production of fuels and commodity chemicals. Yet the application of CO2RR electrolyzers is hampered by low energy and Faradaic efficiencies. Concomitant electrochemical reactions, like hydrogen evolution (HER), lower the selectivity, while the conversion of CO2 into (bi)carbonate through solution acid-base reactions induces an additional concentration overpotential. During CO2RR in aqueous media, the local pH becomes more alkaline than the bulk causing an additional consumption of CO2 by the homogeneous reactions. The latter effect, in combination with the low solubility of CO2 in aqueous electrolytes (33 mM), leads to a significant depletion in CO2 concentration at the electrode surface.The nature of the electrolyte, in terms of pH and cation identity, has recently emerged as an important factor to tune both the energy and Faradaic efficiency. In this Account, we summarize the recent advances in understanding electrolyte effects on CO2RR to CO in aqueous solutions, which is the first, and crucial, step to further reduced products. To compare literature findings in a meaningful way, we focus on results reported under well-defined mass transport conditions and using online analytical techniques. The discussion covers the molecular-level understanding of the effects of the proton donor, in terms of the suppression of the CO2 gradient vs enhancement of HER at a given mass transport rate and of the cation, which is crucial in enabling both CO2RR and HER. These mechanistic insights are then translated into possible implications for industrially relevant cell geometries and current densities.

Effect of pore diameter and length on electrochemical CO2 reduction reaction at nanoporous gold catalysts.

In this work, we employ differential electrochemical mass spectrometry (DEMS) to track the real-time evolution of CO at nanoporous gold (NpAu) catalysts with varying pore parameters (diameter and length) during the electrochemical CO2 reduction reaction (CO2RR). We show that due to the increase in the local pH with increasing catalyst roughness, NpAu catalysts suppress the bicarbonate-mediated hydrogen evolution reaction (HER) compared to a flat Au electrode. Additionally, the geometric current density for CO2RR increases with the roughness of NpAu catalysts, which we attribute to the increased availability of active sites at NpAu catalysts. Together, the enhancement of CO2RR and the suppression of competing HER results in a drastic increase in the faradaic selectivity for CO2RR with increasing pore length and decreasing pore diameter, reaching near 100% faradaic efficiency for CO in the most extreme case. Interestingly, unlike the geometric current density, the specific current density for CO2RR has a more complicated relation with the roughness of the NpAu catalysts. We show that this is due to the presence of ohmic drop effects along the length of the porous channels. These ohmic drop effects render the pores partially electrocatalytically inactive and hence, they play an important role in tuning the CO2RR activity on nanoporous catalysts.

Comparative evaluation of implant stability with and without autologous platelet-rich fibrin prior to prosthetic loading - A split-mouth randomized clinical trial.

Context: Status of bone-implant interface or osseointegration can be assessed by using resonance frequency analysis (RFA), which measures implant stability. A modified implant surface can significantly enhance osseointegration and reduce healing period. Platelet-rich fibrin (PRF) consists of fibrin mesh with entrapped platelets and leukocytes that release a huge number of growth factors which contribute to wound healing and tissue regeneration. Aims: The present study aims to evaluate the effect of PRF on osseointegration in terms of implant stability. Settings and Design: This was a split-mouth randomized clinical trial. Materials and Methods: Sixty surgical sites were divided randomly into two groups. In Group 1 (thirty sites), PRF was placed in osteotomy sites before implant placement whereas no PRF was placed in Group 2 (thirty sites). Stability was measured using RFA in terms of implant stability quotient (ISQ) at baseline, 1 week, 1 month, and 3 months. Statistical Analysis: Intergroup comparison was done using Mann-Whitney U-test. Intragroup comparison was done using Friedman's test followed by pairwise comparison using Wilcoxon signed-rank test. Results: On intergroup comparison, Group 1 showed higher values for ISQ which were statistically significant (P < 0.05) at 1 week and 1 month. No significant difference (P > 0.05) was found at baseline and 3 months. Intragroup comparison and further pairwise comparison revealed a highly significant difference for values between all pairs of time intervals (P < 0.01) with higher values at 3 months. Conclusions: PRF has a significant effect on osseointegration of dental implants during the early healing period prior to loading.

Understanding Cation Trends for Hydrogen Evolution on Platinum and Gold Electrodes in Alkaline Media.

In this work, we study how the cation identity and concentration alter the kinetics of the hydrogen evolution reaction (HER) on platinum and gold electrodes. A previous work suggested an inverted activity trend as a function of alkali metal cation when comparing the performance of platinum and gold catalysts in alkaline media. We show that weakly hydrated cations (K+) favor HER on gold only at low overpotentials (or lower alkalinity), whereas in more alkaline pH (or high overpotentials), a higher activity is observed using electrolytes containing strongly hydrated cations (Li+). We find a similar trend for platinum; however, the inhibition of HER by weakly hydrated cations on platinum is observed already at lower alkalinity and lower cation concentrations, suggesting that platinum interacts more strongly with metal cations than gold. We propose that weakly hydrated cations stabilize the transition state of the water dissociation step more favorably due to their higher near-surface concentration in comparison to a strongly hydrated cation such as Li+. However, at high pH and consequently higher near-surface cation concentrations, the accumulation of these species at the outer Helmholtz plane inhibits HER. This is especially pronounced on platinum, where a change in the rate-determining step is observed at pH 13 when using a Li+- or K+-containing electrolyte.

Understanding the role of mass transport in tuning the hydrogen evolution kinetics on gold in alkaline media.

In this work, we present an in-depth study of the role of mass transport conditions in tuning the hydrogen evolution kinetics on gold by means of rotation rate control. Interestingly, we find that the hydrogen evolution reaction (HER) activity decreases with the increasing rotation rate of the electrode. As we increase the rotation (mass transport) rate, the locally generated hydroxyl ions (2H2O +2e- → H2 + 2OH-) are transported away from the electrode surface at an accelerated rate. This results in decreasing local pH and, because of the need to satisfy local electroneutrality, decreasing near-surface cation concentration. This decrease in the near-surface cation concentration results in the suppression of HER. This is because the cations near the surface play a central role in stabilizing the transition state for the rate determining Volmer step (*H-OHδ--cat+). Furthermore, we present a detailed analytical model that qualitatively captures the observed mass transport dependence of HER solely based on the principle of electroneutrality. Finally, we also correlate the cation identity dependence of HER on gold (Li+ < Na+ < K+) to the changes in the effective concentration of the cations in the double layer with the changes in their solvation energy.

Electrolyte Effects on the Faradaic Efficiency of CO2 Reduction to CO on a Gold Electrode.

The electrochemical reduction of CO2 aims to be a central technology to store excess electricity generated by wind and solar energy. However, the reaction is hindered by the competition with the hydrogen evolution reaction. In this paper, we present a detailed quantitative study of the Faradaic efficiency (FE) to CO on a gold electrode under well-defined mass-transport conditions using rotating ring-disk electrode voltammetry. Varying the concentration of the bicarbonate and the electrolyte cation employing different rotation rates, we map out how these parameters affect the FE(CO). We identify two different potential regimes for the electrolyte effects, characterized by a different dependence on the cation and bicarbonate concentrations. For hydrogen evolution, we analyze the nature of the proton donor for an increasingly negative potential, showing how it changes from carbonic acid to bicarbonate and to water. Our study gives detailed insights into the role of electrolyte composition and mass transport, and helps defining optimized electrolyte conditions for a high FE(CO).

The Interrelated Effect of Cations and Electrolyte pH on the Hydrogen Evolution Reaction on Gold Electrodes in Alkaline Media.

In this work we study the role of alkali metal cation concentration and electrolyte pH in altering the kinetics of the hydrogen evolution reaction (HER) at gold (Au) electrodes. We show that at moderately alkaline pH (pH 11), increasing the cation concentration significantly enhances the HER activity on Au electrodes (with a reaction order ≈0.5). Based on these results we suggest that cations play a central role in stabilizing the transition state of the rate-determining Volmer step by favorably interacting with the dissociating water molecule (*H-OHδ- -cat+ ). Moreover, we show that increasing electrolyte pH (pH 10 to pH 13) tunes the local field strength, which in turn indirectly enhances the activity of HER by tuning the near-surface cation concentration. Interestingly, a too high near-surface cation concentration (at high pH and high cation concentration) leads to a lowering of the HER activity, which we ascribe to a blockage of the surface by near-surface cations.

Suppression of Hydrogen Evolution in Acidic Electrolytes by Electrochemical CO2 Reduction.

In this article we investigate the electrochemical reduction of CO2 at gold electrodes under mildly acidic conditions. Differential electrochemical mass spectroscopy (DEMS) is used to quantify the amounts of formed hydrogen and carbon monoxide as well as the consumed amount of CO2. We investigate how the Faradaic efficiency of CO formation is affected by the CO2 partial pressure (0.1-0.5 bar) and the proton concentration (1-0.25 mM). Increasing the former enhances the rate of CO2 reduction and suppresses hydrogen evolution from proton reduction, leading to Faradaic efficiencies close to 100%. Hydrogen evolution is suppressed by CO2 reduction as all protons at the electrode surfaces are used to support the formation of water (CO2 + 2H+ + 2e- → CO + H2O). Under conditions of slow mass transport, this leaves no protons to support hydrogen evolution. On the basis of our results, we derive a general design principle for acid CO2 electrolyzers to suppress hydrogen evolution from proton reduction: the rate of CO/OH- formation must be high enough to match/compensate the mass transfer of protons to the electrode surface.

Competition between CO2 Reduction and Hydrogen Evolution on a Gold Electrode under Well-Defined Mass Transport Conditions.

Gold is one of the most selective catalysts for the electrochemical reduction of CO2 (CO2RR) to CO. However, the concomitant hydrogen evolution reaction (HER) remains unavoidable under aqueous conditions. In this work, a rotating ring disk electrode (RRDE) setup has been developed to study quantitatively the role of mass transport in the competition between these two reactions on the Au surface in 0.1 M bicarbonate electrolyte. Interestingly, while the faradaic selectivity for CO formation was found to increase with enhanced mass transport (from 67% to 83%), this effect is not due to an enhancement of the CO2RR rate. Remarkably, the inhibition of the competing HER from water reduction with increasing disk rotation rate is responsible for the enhanced CO2RR selectivity. This can be explained by the observation that, on the Au electrode, water reduction improves with more alkaline pH. As a result, the decrease in the local alkalinity near the electrode surface with enhanced mass transport suppresses HER due to the water reduction. Our study shows that controlling the local pH by mass transport conditions can tune the HER rate, in turn regulating the CO2RR and HER competition in the general operating potential window for CO2RR (-0.4 to -1 V vs RHE).