Determining the hydronium pK[Formula: see text] at platinum surfaces and the effect on pH-dependent hydrogen evolution reaction kinetics.

Electrocatalytic hydrogen evolution reaction (HER) is critical for green hydrogen generation and exhibits distinct pH-dependent kinetics that have been elusive to understand. A molecular-level understanding of the electrochemical interfaces is essential for developing more efficient electrochemical processes. Here we exploit an exclusively surface-specific electrical transport spectroscopy (ETS) approach to probe the Pt-surface water protonation status and experimentally determine the surface hydronium pKa [Formula: see text] 4.3. Quantum mechanics (QM) and reactive dynamics using a reactive force field (ReaxFF) molecular dynamics (RMD) calculations confirm the enrichment of hydroniums (H3O[Formula: see text]) near Pt surface and predict a surface hydronium pKa of 2.5 to 4.4, corroborating the experimental results. Importantly, the observed Pt-surface hydronium pKa correlates well with the pH-dependent HER kinetics, with the protonated surface state at lower pH favoring fast Tafel kinetics with a Tafel slope of 30 mV per decade and the deprotonated surface state at higher pH following Volmer-step limited kinetics with a much higher Tafel slope of 120 mV per decade, offering a robust and precise interpretation of the pH-dependent HER kinetics. These insights may help design improved electrocatalysts for renewable energy conversion.

Photothermal Enhancement of Prussian Blue Cathodes for Li-Ion Batteries.

Photoenhanced batteries, where light improves the electrochemical performance of batteries, have gained much interest. Recent reports suggest that light-to-heat conversion can also play an important role. In this work, we study Prussian blue analogues (PBAs), which are known to have a high photothermal heating efficiency and can be used as cathodes for Li-ion batteries. PBAs were synthesized directly on a carbon collector electrode and tested under different thermally controlled conditions to show the effect of photothermal heating on battery performance. Our PBA electrodes reach temperatures that are 14% higher than reference electrodes using a blue LED, and a capacity enhancement of 38% was achieved at a current density of 1600 mA g-1. Additionally, these batteries show excellent cycling stability with a capacity retention of 96.6% in dark conditions and 94.8% in light over 100 cycles. Overall, this work shows new insights into the effects leading to improved battery performance in photobatteries.

Versatile Janus Architecture for Electrocatalytic Applications.

Janus architectures have garnered great research efforts in recent years, leading to outstanding advances in electrocatalysis. Benefiting from the synergistic combination of their anisotropy which endows the manifestation of various co-existing electrochemical properties, and their compartmentalized structure that enables each functional domain to retain its inherent activity, with little to no interference from other domains, Janus architectures show great potential as exceptionally versatile electrocatalysts to complement a plethora of electrocatalytic processes. Thus, coupled with the growing interest in Janus architectures for electrocatalysis, it is imperative to investigate and reconsider their design strategies and future directions.

Recent Progress in Metal Phosphorous Chalcogenides: Potential High-Performance Electrocatalysts.

Since the discovery of graphene, research on the family of 2D materials has been a thriving field. Metal phosphorous chalcogenides (MPX3 ) have attracted renewed attention due to their distinctive physical and chemical properties. The advantages of MPX3 , such as tunable layered structures, unique electronic properties, thermodynamically appropriate band alignments and abundant catalytic active sites on the surface, make MPX3 material great potential in electrocatalysis. In this review, the applications of MPX3 electrocatalysts in recent years, including hydrogen evolution reaction, oxygen evolution reaction, and oxygen reduction reaction, are summarized. Structural regulation, chemical doping and multi-material composite that are often effective and practical research methods to further optimize the catalytic properties of these materials, are introduced. Finally, the challenges and opportunities for electrocatalytic applications of MPX3 materials are discussed. This report aims to advance future efforts to develop MPX3 and related materials for electrocatalysis.

Mechanistic Insight into Electrode Processes by Operando Visualization of Interfacial pH Using Fluorescent Nanosensors.

Operando visualization of interfacial pH is crucial, yet challenging in electrochemical processes. Herein, we report the fabrication and utilization of ratiometric, fluorescent pH-sensitive nanosensors for operando quantification of fast-dynamic, interfacial pH changes in electrochemical processes and environments where unprotected fluorescent dyes would be degraded. Spatio-temporal pH changes were detected using an electrochemically coupled laser scanning confocal microscope (EC-LSCM) during the electrocoagulation treatment of model and field samples of oil-sands-produced water. Operando visualization of interfacial pH provided new insights into the electrode processes, including ion speciation, electrode fouling, and Faradaic efficiency. We provide compelling evidence that formed metal complexes precipitate at the edge of the pH boundary layer and that there is a strong coupling between the thickness of the interfacial pH layer and the electrode fouling. Furthermore, these findings provide a powerful pathway for optimizing the operating conditions, minimizing electrode passivation, and enhancing the efficiency of electrochemical processes, e.g., electrocoagulation, flow batteries, capacitive deionization, and electrolyzes.

Metal-Based Aerogels Catalysts for Electrocatalytic CO2 Reduction.

General strategies for metal aerogel synthesis, including single-metal, transition-metal doped, multi-metal-doped, and nano-metal-doped carbon aerogel are described. In addition, the latest applications of several of the above-mentioned metal aerogels in electrocatalytic CO2 reduction are discussed. Finally, considering the possibility of future applications of electrocatalytic CO2 reduction technology, a vision for industrialization and directions that can be optimized are proposed.

Ligand "noninnocence" in coordination complexes vs. kinetic, mechanistic, and selectivity issues in electrochemical catalysis.

The world of coordination complexes is currently stimulated by the quest for efficient catalysts for the electrochemical reactions underlying modern energy and environmental challenges. Even in the case of a multielectron-multistep process, catalysis starts with uptake or removal of one electron from the resting state of the catalyst. If this first step is an outer-sphere electron transfer (triggering a "redox catalysis" process), the electron distribution over the metal and the ligand is of minor importance. This is no longer the case with "chemical catalysis," in which the active catalyst reacts with the substrate in an inner-sphere manner, often involving the transient formation of a catalyst-substrate adduct. The fact that, in most cases, the ligand is "noninnocent," in the sense that the electron density and charge gained (or removed) from the resting state of the catalyst are shared between the metal and the ligand, has become common-place knowledge over the last half-century. Insistent focus on a large degree of noninnocence of the ligand in the resting state of the catalyst, even robustly validated by spectroscopic techniques, may lead to undermining the essential role of the metal when such essential issues as kinetics, mechanisms, and product selectivity are dealt with. These points are general in scope, but their discussion is eased by adequately documented examples. This is the case for reactions involving metalloporphyrins as well as vitamin B12 derivatives and similar cobalt complexes for which a wealth of experimental data is available.

Enabling Lithium Metal Anode in Nonflammable Phosphate Electrolyte with Electrochemically Induced Chemical Reactions.

Lithium metal anode holds great promises for next-generation battery technologies but is notoriously difficult to work with. The key to solving this challenge is believed to lie in the ability of forming stable solid-electrolyte interphase (SEI) layers. To further address potential safety issues, it is critical to achieve this goal in nonflammable electrolytes. Building upon previous successes in forming stable SEI in conventional carbonate-based electrolytes, here we report that reversible Li stripping/plating could be realized in triethyl phosphate (TEP), a known flame retardant. The critical enabling factor of our approach was the introduction of oxygen, which upon electrochemical reduction induces the initial decomposition of TEP and produces Li3 PO4 and poly-phosphates. Importantly, the reaction was self-limiting, and the resulting material regulated Li plating by limiting dendrite formation. In effect, we obtained a functional SEI on Li metal in a nonflammable electrolyte. When tested in a symmetric Li∥Li cell, more than 300 cycles of stripping/plating were measured at a current density of 0.5 mA cm-2 . Prototypical Li-O2 and Li-ion batteries were also fabricated and tested to further support the effectiveness of this strategy. The mechanism by which the SEI forms was studied by density functional theory (DFT), and the predictions were corroborated by the successful detection of the intermediates and products.

Proton Relays in Molecular Catalysis of Electrochemical Reactions: Origin and Limitations of the Boosting Effect.

Homogeneous catalysis of electrochemical reactions, related to contemporary energy challenges, often involves proton-coupled electron transfer sequences. The idea rapidly emerged that installing the proton donor (for reductions, or acceptor for oxidations) inside the catalyst molecule should be beneficial in terms of efficiency, as it would then be closer to the nerve center of the process (usually the metal in the case of transition metal complex catalysts). If this proton relay has indeed done the job, it has lost its proton at the end of each catalytic loop, and must therefore be reprotonated (for reductions, or deprotonated for oxidations) from acid (or base) from the solution before a new catalytic loop can start. The impression may thus be that there is a zero-sum game. The conditions under which this is not the case may entail, in contrast, a considerable boosting of catalysis. This will also allow explain why the proton is such a specifically appropriate agent for this task.

Sulfur-Rich Phosphorus Sulfide Molecules for Use in Rechargeable Lithium Batteries.

A new family of sulfur-rich phosphorus sulfide molecules (P4 S10+n ) and their electrochemical reaction mechanism with metallic Li has been explored. These P4 S10+n molecules are synthesized by the reaction between P4 S10 and S. For Li batteries, the P4 S40 molecule in the series of P4 S10+n molecules provides the highest capacity, which has a first discharge capacity of 1223 mAh g-1 at 100 mA g-1 and stabilizes at approximately 720 mAh g-1 at 500 mA g-1 after 100 cycles. This new class of sulfur-rich P4 S10+n molecules and its electrochemical behavior for room-temperature Li+ storage could provide novel insights for phosphorus sulfide molecules and high-energy batteries.

Coupling Electrochemistry with Probe Electrospray Ionization Mass Spectrometry.

A new coupling of electrochemistry with mass spectrometry (MS) using probe electrospray ionization (PESI) is presented. Due to the high salt tolerance of PESI, the detection of electrochemical reaction products in room-temperature ionic liquids (RTILs) is realized for the first time. Furthermore, PESI-MS allows the analysis of electrochemical reaction products on different or multiple electrode surfaces. In addition, peptides and proteins fractionated through isoelectric focusing (IEF) in the presence of an external electric field can also be directly analyzed by using PESI-MS, suggesting a new and rapid characterization means for the IEF technique. This study reveals the versatility of EC/PESI-MS, which could have an impact in electrochemistry and bioanalysis fields.

Rapid measurement of bacterial contamination in water: A catalase responsive-electrochemical sensor.

The present study describes the development of a potentiometric sensor for microbial monitoring in water based on catalase activity. The sensor comprises a MnO2-modified electrode that responds linearly to hydrogen peroxide (H2O2) from 0.16 M to 3.26 M. The electrode potential drops when the H2O2 solution is spiked with catalase or catalase-producing microorganisms that decompose H2O2. The sensor is responsive to different bacteria and their catalase activities. The electrochemical sensor exhibits a lower limit of detection (LOD) for Escherichia coli at 11 CFU/ml, Citrobacter youngae at 12 CFU/ml, and Pseudomonas aeruginosa at 23 CFU/ml. The sensor shows high sensitivity at 3.49, 3.02, and 4.24 mV/cm2dec for E. coli, C. youngae, and P. aeruginosa, respectively. The abiotic sensing electrode can be used multiple times without changing the response potential (up to 100 readings) with a shelf-life of over six months. The response time is a few seconds, with a total test time of 5 min. Additionally, the sensor effectively tested actual samples (drinking and grey water), which makes it a quick and reliable sensing tool. Therefore, the study offers a promising water monitoring tool with high sensitivity, stability, good detection limit, and minimum interference from other water contaminants.

Applications of electron microscopic observations to electrochemistry in liquid electrolytes for batteries.

Herein, we review notable points from observations of electrochemical reactions in a liquid electrolyte by liquid-phase electron microscopy. In situ microscopic observations of electrochemical reactions are urgently required, particularly to solve various battery issues. Battery performance is evaluated by various electrochemical measurements of bulk samples. However, it is necessary to understand the physical/chemical phenomena occurring in batteries to elucidate the reaction mechanisms. Thus, in situ microscopic observation is effective for understanding the reactions that occur in batteries. Herein, we focus on two methods, of the liquid phase (scanning) transmission electron microscopy and liquid phase scanning electron microscopy, and summarize the advantages and disadvantages of both methods.

Targeted synthesis of a metal-free thiadiazolate based nitrogen and sulfur rich porous organic polymer for an unprecedented hydrogen evolution in the electrochemical water splitting.

Water splitting is a long-standing quest to material research for mitigating the global energy crisis. Despite high efficiency shown by several high cost noble metal containing electrocatalysts in the water splitting reaction, scientists are focused on alternate metal-free carbon or polymer based materials with comparable activity to make the process economical. In this article, we have strategically designed a noble metal-free thiadiazole (TDA) and triazine (Trz) linked porous organic polymer (TDA-Trz-POP) having N- and S-rich surface. Powder X-ray diffraction (PXRD), Fourier transform infrared (FT-IR), solid state 13C magic angle spinning nuclear magnetic resonance (MAS-NMR) and X-ray photoelectron spectroscopic (XPS) analyses have been performed to predict its probable framework structure. This scrunch paper type TDA-Trz-POP shows an extravagant potential for the hydrogen evolution reaction (HER) with a low overpotential (129.2 mV w.r.t. RHE for 10 mA cm-2 current density) and low Tafel slope (82.1 mV deg-1). Again, this metal-free catalyst shows oxygen evolution reaction (OER) at 410 mV overpotential w.r.t RHE for 10 mA cm-2 current density with a lower Tafel slope of 104.5 mV deg-1. This bifunctional activity was further tested in two electrodes set-up under different pH conditions. The porosity seems to be a blessing in the electrocatalytic performance of this metal-free electrocatalyst material. Further, the mystery behind the activity of both HER and OER has been resolved through the density functional theory (DFT) analysis. This work provides an insight to the material scientists for low cost, metal-free material design for the efficient water splitting reaction.

Advances in Electrochemical Liquid-Phase Transmission Electron Microscopy for Visualizing Rechargeable Battery Reactions.

This review presents an overview of the application of electrochemical liquid-phase transmission electron microscopy (ELP-TEM) in visualizing rechargeable battery reactions. The technique provides atomic-scale spatial resolution and real-time temporal resolution, enabling direct observation and analysis of battery materials and processes under realistic working conditions. The review highlights key findings and insights obtained by ELP-TEM on the electrochemical reaction mechanisms and discusses the current limitations and future prospects of ELP-TEM, including improvements in spatial and temporal resolution and the expansion of the scope of materials and systems that can be studied. Furthermore, the review underscores the critical role of ELP-TEM in understanding and optimizing the design and fabrication of high-performance, long-lasting rechargeable batteries.

Recent catalytic applications of MXene-based layered nanomaterials.

The urgent issues related to the catalytic processes and energy applications have accelerated the development of hybrid and smart materials. MXenes are a new family of atomic layered nanostructured materials that require considerable research. Tailorable morphologies, strong electrical conductivity, great chemical stability, large surface-to-volume ratios, tunable structures, among others are some significant characteristics that make MXenes appropriate for various electrochemical reactions, including dry reforming of methane, hydrogen evolution reaction, methanol oxidation reaction, sulfur reduction reaction, Suzuki-Miyaura coupling reaction, water-gas shift reaction, and so forth. MXenes, on the other hand, have a fundamental drawback of agglomeration, as well as poor long-term recyclability and stability. One possibility for overcoming the restrictions is the fusion of nanosheets or nanoparticles with MXenes. Herein, the relevant literature on the synthesis, catalytic stability and reusability, and applications of several MXene-based nanocatalysts are deliberated including the merits and cons of the newer MXene-based catalysts.

The Use of Redox Mediators in Electrocatalysis and Electrosynthesis.

Electrocatalysis and electrosynthesis, which convert the electrical energy and store them in the chemical forms, have been considered as promising technologies to utilize green renewable energy sources. Most of the studies focused on developing novel active molecules or advanced electrodes to improve the performance. However, the direct acquisition and electron transferring will be limited by the intrinsic characters of the electrodes. The introduce of redox mediators, which are served as the intermediate electron carriers or reservoirs without changing the final products, provide a unique approach to accelerate the electrochemical performance of these energy conversions. This review provides an overview of the recent development of electrocatalysis and electrosynthesis by using redox mediators, and provides a comprehensive discussion toward focusing on the principles and construction of these systems.

Effect of polarity reversal on floc formation and rheological properties of a sludge formed by the electrocoagulation process.

Anode fouling is one of the key limiting factors to the widespread application of electrocoagulation (EC) for treatment of different types of contaminated water. Promising mitigation strategy to fouling is to operate the process under polarity reversal (PR) instead of direct current (DC). However, the PR operation comes at the cost of process complexity due to the alternation of electrochemical and chemical reactions. In this study, we systematically investigated the link between evolving fouling layer during DC and PR close to iron and aluminum electrodes and morphological and rheological properties of the formed sludge. By operando visualization of EC process, we demonstrate that during PR operation, precipitation of the iron and aluminum species occurs close to the anode interface, resulting in flocs with higher porosity and lower density than those formed under DC conditions. However, rheological investigation revealed that the PR conditions resulted in a sludge with more pronounced solid-like signature, but this enhancement in its viscoelastic properties is closely related to a period of the current's polarity reversal. We attribute this unexpected result to higher shear rate and collision of particles during PR conditions.

Low Temperature Nano Mechano-electrocatalytic CH4 Conversion.

Transforming natural resources to energy sources, such as converting CH4 to H2 and carbon, at high efficiency and low cost is crucial for many industries and environmental sustainability. The high temperature requirement of CH4 conversion regarding many of the current methods remains a critical bottleneck for their practical uptake. Here we report an approach based on gallium (Ga) liquid metal droplets, Ni(OH)2 cocatalysts, and mechanical energy input that offers low-temperature and scalable CH4 conversion into H2 and carbon. Mainly driven by the triboelectric voltage, originating from the joint contributions of the cocatalysts during agitation, CH4 is converted at the Ga and Ni(OH)2 interface through nanotribo-electrochemical reaction pathways. The efficiency of the system is enhanced when the reaction is performed at an increased pressure. The dehydrogenation of other nongaseous hydrocarbons using this approach is also demonstrated. This technology presents a possible low energy route for CH4 conversion without involving high temperature and harsh operating conditions.

Visualization of electrochemical reactions on microelectrodes using light-addressable potentiometric sensor imaging.

Visualization of the electrochemical reaction is essential for comprehensively understanding the electrochemical reaction mechanism and precisely characterizing dynamic electrochemical processes. Herein, we propose a simple device that combines light-addressable potentiometric sensor (LAPS) imaging and microelectrodes to serve as a general electroanalysis platform for the label-free sensing and imaging of electrochemical reactions. In this device, two microelectrodes are assembled on the LAPS chip. Electrochemical reactions occurring on the microelectrodes can be qualitatively and quantitatively observed and visualized using a LAPS chip that is sensitive to the reaction products. Validations were performed to monitor the effect of water electrolysis and potassium ferrocyanide oxidation surrounding the microelectrodes, respectively. We believe that this study will provide an excellent platform for the visualization and monitoring of electrochemical reactions and broaden the application scope of LAPS imaging to a general electroanalysis tool that is widely applicable in several fields.