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Nickel-based oxides and oxyhydroxide catalysts exhibit state-of-the-art activity for the sluggish oxygen evolution reaction (OER) under alkaline conditions. A widely employed strategy to increase the gravimetric activity of the catalyst is to increase the active surface area via nanostructuring or decrease the particle size. However, the fundamental understanding about how tuning these parameters influences the density of oxidized species and their reaction kinetics remains unclear. Here, we use solution combustion synthesis, a low-cost and scalable approach, to synthesize a series of Fe0.1Ni0.9O samples from different precursor salts. Based on the precursor salt, the nanoparticle size can be changed significantly from ∼2.5 to ∼37 nm. The OER activity at pH 13 trends inversely with the particle size. Using operando time-resolved optical spectroscopy, we quantify the density of oxidized species as a function of potential and demonstrate that the OER kinetics exhibits a second-order dependence on the density of these species, suggesting that the OER mechanism relies on O-O coupling between neighboring oxidized species. With the decreasing particle size, the density of species accumulated is found to increase, and their intrinsic reactivity for the OER is found to decrease, attributed to the stronger binding of *O species (i.e., a cathodic shift of species energetics). This signifies that the high apparent OER activity per geometric area of the smaller nanoparticles is driven by their ability to accumulate a larger density of oxidized species. This study not only experimentally disentangles the influence of the density of oxidized species and intrinsic kinetics on the overall rate of the OER but also highlights the importance of tuning these parameters independently to develop more active OER catalysts.

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Electrochemical nitrate (NO3-) reduction to ammonia (NH3), which is a high value-added chemical or high-energy density carrier in many applications, could become a key process overcoming the disadvantages of the Haber-Bosch process; however, current electrocatalysts have severe drawbacks in terms of activity, selectivity, and stability. Here, we report the hydrogen radical (H*) pathway as a solution to overcome this challenge, as demonstrated by efficacious electrochemical NO3- reduction to NH3 over the Fe-polyoxometalate (Fe-POM)/Cu hybrid electrocatalyst. Fe-POM, composed of Preyssler anions ([NaP5W30O110]14-) and Fe cations, facilitates efficient H* generation via H2O + e- → H* + OH-, and H* transfer to the Cu sites of the Fe-POM/Cu catalyst enables selective NO3- reduction to NH3. Operando spectroelectrochemical spectra substantiate the occurrence of the H* pathway through direct observation of Fe redox related to H* generation and Cu redox related to NO3- binding. With the H* pathway, the Fe-POM/Cu electrodes exhibit high activity for NO3- reduction to NH3 with 1.44 mg cm-2 h-1 in a 500 ppm NO3-/1 M KOH solution at -0.2 V vs. RHE, which is about 36-fold higher than that of the pristine Cu electrocatalyst. Additionally, it attains high selectivity with a faradaic efficiency of up to 97.09% at -0.2 V vs. RHE while exhibiting high catalytic stability over cycles.

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A barrier to understanding the factors driving catalysis in the oxygen evolution reaction (OER) is understanding multiple overlapping redox transitions in the OER catalysts. The complexity of these transitions obscure the relationship between the coverage of adsorbates and OER kinetics, leading to an experimental challenge in measuring activity descriptors, such as binding energies, as well as adsorbate interactions, which may destabilize intermediates and modulate their binding energies. Herein, we utilize a newly designed optical spectroelectrochemistry system to measure these phenomena in order to contrast the behavior of two electrocatalysts, cobalt oxyhydroxide (CoOOH) and cobalt-iron hexacyanoferrate (cobalt-iron Prussian blue, CoFe-PB). Three distinct optical spectra are observed in each catalyst, corresponding to three separate redox transitions, the last of which we show to be active for the OER using time-resolved spectroscopy and electrochemical mass spectroscopy. By combining predictions from density functional theory with parameters obtained from electroadsorption isotherms, we demonstrate that a destabilization of catalytic intermediates occurs with increasing coverage. In CoOOH, a strong (∼0.34 eV/monolayer) destabilization of a strongly bound catalytic intermediate is observed, leading to a potential offset between the accumulation of the intermediate and measurable O2 evolution. We contrast these data to CoFe-PB, where catalytic intermediate generation and O2 evolution onset coincide due to weaker binding and destabilization (∼0.19 eV/monolayer). By considering a correlation between activation energy and binding strength, we suggest that such adsorbate driven destabilization may account for a significant fraction of the observed OER catalytic activity in both materials. Finally, we disentangle the effects of adsorbate interactions on state coverages and kinetics to show how adsorbate interactions determine the observed Tafel slopes. Crucially, the case of CoFe-PB shows that, even where interactions are weaker, adsorption remains non-Nernstian, which strongly influences the observed Tafel slope.

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Understanding the effect of noncovalent interactions of intermediates at the polarized catalyst-electrolyte interface on water oxidation kinetics is key for designing more active and stable electrocatalysts. Here, we combine operando optical spectroscopy, X-ray absorption spectroscopy (XAS), and surface-enhanced infrared absorption spectroscopy (SEIRAS) to probe the effect of noncovalent interactions on the oxygen evolution reaction (OER) activity of IrOx in acidic and alkaline electrolytes. Our results suggest that the active species for the OER (Ir4.x+-*O) binds much stronger in alkaline compared with acid at low coverage, while the repulsive interactions between these species are higher in alkaline electrolytes. These differences are attributed to the larger fraction of water within the cation hydration shell at the interface in alkaline electrolytes compared to acidic electrolytes, which can stabilize oxygenated intermediates and facilitate long-range interactions between them. Quantitative analysis of the state energetics shows that although the *O intermediates bind more strongly than optimal in alkaline electrolytes, the larger repulsive interaction between them results in a significant weakening of *O binding with increasing coverage, leading to similar energetics of active states in acid and alkaline at OER-relevant potentials. By directly probing the electrochemical interface with complementary spectroscopic techniques, our work goes beyond conventional computational descriptors of the OER activity to explain the experimentally observed OER kinetics of IrOx in acidic and alkaline electrolytes.

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The molecule-metal interface is of paramount importance for many devices and processes, and directly involved in photocatalysis, molecular electronics, nanophotonics, and molecular (bio-)sensing. Here the photostability of this interface is shown to be sensitive even to room light levels for specific molecules and metals. Optical spectroscopy is used to track photoinduced migration of gold atoms when functionalised with different thiolated molecules that form uniform monolayers on Au. Nucleation and growth of characteristic surface metal nanostructures is observed from the light-driven adatoms. By watching the spectral shifts of optical modes from nanoparticles used to precoat these surfaces, we identify processes involved in the photo-migration mechanism and the chemical groups that facilitate it. This photosensitivity of the molecule-metal interface highlights the significance of optically induced surface reconstruction. In some catalytic contexts this can enhance activity, especially utilising atomically dispersed gold. Conversely, in electronic device applications such reconstructions introduce problematic aging effects.

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BACKGROUND: The usage of smartphones has become common among adolescents, despite knowing the health-related problems of the user. Currently, the availability of electronic gadgets has become economical and this has an impact on society, especially on the behavior of adolescents. MATERIALS AND METHODS: A cross-sectional survey design was used to find the pattern of smartphone usage, smartphone addiction, and subjective health problems associated with smartphone usage. The data were obtained from 270 nursing students using the convenient sampling technique using a sociodemographic proforma, semi-structured questionnaire on the pattern of smartphone usage, Smartphone Addiction Scale, self-reported subjective health problems questionnaire, and study habits scale. STATISTICAL ANALYSIS: Descriptive and inferential statistics was used for the analysis using SPSS 16.0. RESULTS: The study findings revealed that most of the participants 243 (90.0%) were using 4G phones. The majority 88 (32.60%) of the participants were using a smartphone for less than 2 hours at a stretch in a day. Most uses of a smartphone were in the night 155 (57.40%). The main usage of a smartphone was for entertainment purposes 213 (78.90%). Most of the participants 196 (72.6%) were moderately addicted to smartphones. One-third 109 (40.2%) of the participants complained of headache, followed by straining of the eyes 83 (30.6%). CONCLUSION: The awareness of smartphone addiction and health-related problems associated with smartphone usage has been shown to decrease its impact. The study concluded that it is very much necessary to identify the pattern of smartphone usage, to prevent the consequences of addiction and health problems associated with smartphone usage.

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In the present study, we describe a facile strategy for the easy removal of the heavy metal ion, Pb (II) using biosynthesized copper ferrite (CuFe2O4) Nanoparticles (Nps) prepared via a cost-effective and eco-friendly method usingPimenta dioicaleaf extract. The structural characterization was performed using UV-Visible, FT-IR, XRD, XPS, TG, SEM - EDS and TEM techniques. Various characterization techniques showed that the biosynthesized CuFe2O4nanoparticles have spherical shape with minimum aggregation and possess a size range between 7 and 16 nm. Batch experiments were carried out to analyze the adsorption efficiency of CuFe2O4Nps by varying different experimental conditions such as pH, adsorbent dose and initial metal ion concentration. From the atomic absorption spectroscopy results, the optimum removal efficiency (99.69%) occurred at a contact time of 90 min in the solution having pH 6 with 0.06 g of nanoadsorbent. The experimental data were analyzed using adsorption isotherm and fitted with kinetic models. In the present study, we report the the highest removal efficiency of 99.69% for Pb (II) ions with minimum experimental parameters which is greater than other similar reported studies. The novel CuFe2O4nanosorbent synthesized in the present study is highly effective in eliminating toxic pollutants. They also possess outstanding recycling characteristics for the effective removal of Pb (II) ions from aqueous media.This cost-effective and ecofriendly strategy could be utilized for addressing the emerging water contamination.

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PURPOSE OF REVIEW: There is a paucity of evidence for managing perioperative anticoagulation in patients with cancer. This review aims to provide clinicians who provide care for patients with cancer an overview of the available information and strategies needed to provide optimal care in a perioperative setting. RECENT FINDINGS: There is new evidence available around the management of perioperative anticoagulation in patients with cancer. The new literature and guidance were analyzed and summarized in this review. Management of perioperative anticoagulation in individuals with cancer is a challenging clinical dilemma. The approach to managing anticoagulation requires clinicians to review both disease and treatment specific patient factors that can contribute to both thrombotic and bleed risks. A thorough patient-specific assessment is essential in ensuring patients with cancer receive appropriate care in the perioperative setting.

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Pt-based bimetallic electrocatalysts are promising candidates to convert surplus glycerol from the biodiesel industry to value-added chemicals and coproduce hydrogen. It is expected that the nature and content of the elements in the bimetallic catalyst can not only affect the reaction kinetics but also influence the product selectivity, providing a way to increase the yield of the desired products. Hence, in this work, we investigate the electrochemical oxidation of glycerol on a series of PtNi nanoparticles with increasing Ni content using a combination of physicochemical structural analysis, electrochemical measurements, operando spectroscopic techniques, and advanced product characterizations. With a moderate Ni content and a homogenously alloyed bimetallic Pt-Ni structure, the PtNi2 catalyst displayed the highest reaction activity among all materials studied in this work. In situ FTIR data show that PtNi2 can activate the glycerol molecule at a more negative potential (0.4 V RHE) than the other PtNi catalysts. In addition, its surface can effectively catalyze the complete C-C bond cleavage, resulting in lower CO poisoning and higher stability. Operando X-ray absorption spectroscopy and UV-vis spectroscopy suggest that glycerol adsorbs strongly onto surface Ni(OH) x sites, preventing their oxidation and activation of oxygen or hydroxyl from water. As such, we propose that the role of Ni in PtNi toward glycerol oxidation is to tailor the electronic structure of the pure Pt sites rather than a bifunctional mechanism. Our experiments provide guidance for the development of bimetallic catalysts toward highly efficient, selective, and stable glycerol oxidation reactions.

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India was severely affected by the second wave of coronavirus disease (COVID­19), leading to sudden expansive spread of Mucormycosis, presenting with sinusitis, blackish mucus secretions, discolouration of palate, facial pain, swelling and blurring of vision. Hyperglycemia, hypercoagulable state and elevated levels of serum ferritin were the major contributing factors in progression of the deadly disease. To highlight the correlation between Diabetes Mellitus, hyperferritenimia and elevated levels of D-Dimer with increased rate of incidence and poor prognosis of the disease. This study was undertaken in KLES Dr Prabhakar Kore Hospital & MRC, Belagavi, including 30 patients, between April to July 2021. Serum ferritin, HbA1C and D-Dimer were evaluated for patients on admission, along with the other routine blood investigations. The mean age was 50 years (49.99 ± 1.8), with a male predominance of 83.33% (25 Male patients). 93.33% patients had uncontrolled Diabetes Mellitus with a mean value of 10.12% (± 0.37) indicating Diabetes Mellitus to be the prime risk factor. The raised levels of serum ferritin with a mean of 662.01 ng/ml (± 129.18) and high levels of D-Dimer (Mean- 761.33 ± 151.8 ng/ml) also demonstrated their role as interlinked factors. Mucor epidemic was caused by convergence of interlinked risk factors. Awareness of red flag clinical features, prompt diagnosis, early initiation of treatment with amphotericin-B with aggressive surgical debridement are essential for successful outcome, to avoid high rate of mortality and morbidity rates in the mucormycosis patients.

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The operating conditions of low pH and high potential at the anodes of polymer electrolyte membrane electrolysers restrict the choice of catalysts for the oxygen evolution reaction (OER) to oxides based on the rare metals iridium or ruthenium. In this work, we investigate the stability of both the metal atoms and, by quantitative and highly sensitive 18O isotope labelling experiments, the oxygen atoms in a series of RuO x and IrO x electrocatalysts during the OER in the mechanistically interesting low overpotential regime. We show that materials based on RuO x have a higher dissolution rate than the rate of incorporation of labelled oxygen from the catalyst into the O2 evolved ("labelled OER"), while for IrO x -based catalysts the two rates are comparable. On amorphous RuO x , metal dissolution and labelled OER are found to have distinct Tafel slopes. These observations together lead us to a full mechanistic picture in which dissolution and labelled OER are side processes to the main electrocatalytic cycle. We emphasize the importance of quantitative analysis and point out that since less than 0.2% of evolved oxygen contains an oxygen atom originating from the catalyst itself, lattice oxygen evolution is at most a negligible contribution to overall OER activity for RuO x and IrO x in acidic electrolyte.

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The high overpotential required for the oxygen evolution reaction (OER) represents a significant barrier for the production of closed-cycle renewable fuels and chemicals. Ruthenium dioxide is among the most active catalysts for OER in acid, but the activity at low overpotentials can be difficult to measure due to high capacitance. In this work, we use electrochemistry - mass spectrometry to obtain accurate OER activity measurements spanning six orders of magnitude on a model series of ruthenium-based catalysts in acidic electrolyte, quantifying electrocatalytic O2 production at potential as low as 1.30 VRHE. We show that the potential-dependent O2 production rate, i.e., the Tafel slope, exhibits three regimes, revealing a previously unobserved Tafel slope of 25 mV decade-1 below 1.4 VRHE. We fit the expanded activity data to a microkinetic model based on potential-dependent coverage of the surface intermediates from which the rate-determining step takes place. Our results demonstrate how the familiar quantities "onset potential" and "exchange current density" are influenced by the sensitivity of the detection method.

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Water oxidation is the step limiting the efficiency of electrocatalytic hydrogen production from water. Spectroelectrochemical analyses are employed to make a direct comparison of water oxidation reaction kinetics between a molecular catalyst, the dimeric iridium catalyst [Ir2(pyalc)2(H2O)4-(µ-O)]2+ (IrMolecular, pyalc = 2-(2'pyridinyl)-2-propanolate) immobilized on a mesoporous indium tin oxide (ITO) substrate, with that of an heterogeneous electrocatalyst, an amorphous hydrous iridium (IrOx) film. For both systems, four analogous redox states were detected, with the formation of Ir(4+)-Ir(5+) being the potential-determining step in both cases. However, the two systems exhibit distinct water oxidation reaction kinetics, with potential-independent first-order kinetics for IrMolecular contrasting with potential-dependent kinetics for IrOx. This is attributed to water oxidation on the heterogeneous catalyst requiring co-operative effects between neighboring oxidized Ir centers. The ability of IrMolecular to drive water oxidation without such co-operative effects is explained by the specific coordination environment around its Ir centers. These distinctions between molecular and heterogeneous reaction kinetics are shown to explain the differences observed in their water oxidation electrocatalytic performance under different potential conditions.

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Metal oxides and oxyhydroxides exhibit state-of-the-art activity for the oxygen evolution reaction (OER); however, their reaction mechanism, particularly the relationship between charging of the oxide and OER kinetics, remains elusive. Here, we investigate a series of Mn-, Co-, Fe-, and Zn-doped nickel oxides using operando UV-vis spectroscopy coupled with time-resolved stepped potential spectroelectrochemistry. The Ni2+/Ni3+ redox peak potential is found to shift anodically from Mn- < Co- < Fe- < Zn-doped samples, suggesting a decrease in oxygen binding energetics from Mn- to Zn-doped samples. At OER-relevant potentials, using optical absorption spectroscopy, we quantitatively detect the subsequent oxidation of these redox centers. The OER kinetics was found to have a second-order dependence on the density of these oxidized species, suggesting a chemical rate-determining step involving coupling of two oxo species. The intrinsic turnover frequency per oxidized species exhibits a volcano trend with the binding energy of oxygen on the Ni site, having a maximum activity of ∼0.05 s-1 at 300 mV overpotential for the Fe-doped sample. Consequently, we propose that for Ni centers that bind oxygen too strongly (Mn- and Co-doped oxides), OER kinetics is limited by O-O coupling and oxygen desorption, while for Ni centers that bind oxygen too weakly (Zn-doped oxides), OER kinetics is limited by the formation of oxo groups. This study not only experimentally demonstrates the relation between electroadsorption free energy and intrinsic kinetics for OER on this class of materials but also highlights the critical role of oxidized species in facilitating OER kinetics.

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A large-scale mortality of pearlspot, Etroplus suratensis was reported from Peechi Dam, an artificial tropical lake made for irrigation and drinking water supply in Kerala, India during 2018. This dam is located in the premises of Western Ghats, recognized as one of the biodiversity hotspots of the world. The objective of this study was to identify the aetiological agent of this large-scale mortality of E. suratensis by systematic diagnostic investigation and identification of the pathogen. Virus isolation was carried out on a species-specific pearlspot fin (PSF) cell line. Infected PSF cells showed cytopathic effects (CPEs) like cell shrinkage, rounding, enlargement, clustering, and subsequent detachment of cells with a high viral titre of 106⋅95 TCID50 ml-1 at 8 days post-inoculation (dpi). Histopathological examination of the fish showed the presence of numerous abnormal enlarged basophilic cells and intracytoplasmic eosinophilic inclusions in the liver. Moreover, transmission electron microscopy (TEM) analysis revealed the presence of large numbers of 125-132 nm viral particles in the spleen tissues. PCR amplification and phylogenetic analysis of the major capsid protein (MCP) gene sequence confirmed that the causative agent was infectious spleen and kidney necrosis virus (ISKNV) of the genus Megalocytivirus. The experimental infection recorded 86.7 ± 2.7% mortality in the E. suratensis (body weight 11.01 ± 2.7 g; body length 8.01 ± 2.23 cm) injected with 1 × 104⋅25 TCID50 ml-1 ISKNV per fish. Our detailed investigation provided definitive diagnosis of ISKNV in the severe mass mortality event in wild E. suratensis in Peechi Dam, India, adding one more species to expanding host range of ISKNV infection. The high mortality rate of ISKNV infection in pearlspot suggests the perilous nature of this disease, particularly among the wild fish population.

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Hundreds of genetic variants in KCNQ2 encoding the voltage-gated potassium channel KV7.2 are associated with early onset epilepsy and/or developmental disability, but the functional consequences of most variants are unknown. Absent functional annotation for KCNQ2 variants hinders identification of individuals who may benefit from emerging precision therapies. We employed automated patch clamp recordings to assess at, to our knowledge, an unprecedented scale the functional and pharmacological properties of 79 missense and 2 inframe deletion KCNQ2 variants. Among the variants we studied were 18 known pathogenic variants, 24 mostly rare population variants, and 39 disease-associated variants with unclear functional effects. We analyzed electrophysiological data recorded from 9,480 cells. The functional properties of 18 known pathogenic variants largely matched previously published results and validated automated patch clamp for this purpose. Unlike rare population variants, most disease-associated KCNQ2 variants exhibited prominent loss-of-function with dominant-negative effects, providing strong evidence in support of pathogenicity. All variants responded to retigabine, although there were substantial differences in maximal responses. Our study demonstrated that dominant-negative loss-of-function is a common mechanism associated with missense KCNQ2 variants. Importantly, we observed genotype-dependent differences in the response of KCNQ2 variants to retigabine, a proposed precision therapy for KCNQ2 developmental and epileptic encephalopathy.

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Necrotizing fasciitis is severe inflammation of the muscle sheath that leads to necrosis of the subcutaneous tissue and adjacent fascia. The disease entity is more commonly described in adults and the literature seems quite sparse with respect to children and even lesser in neonates. Monomicrobial infection with necrotizing fasciitis in Neck following insect bite is rare and even rarer in neonates. 07 day old neonate had history of rapid onset discoloration and swelling of the Right side of Neck following an insect bite which was followed fever and irritability and eventually black discoloration. The neonate was irritable with excessive crying, had tachycardia, tachypnea and was febrile. There was a diffuse swelling in the right side of neck with multiple patchy areas of tissue necrosis in form of blackening of the skin over the swelling Management: Necrotizing fasciitis was identified early and the neonate prepped for surgery. All the biochemical parameters were WNL. CRP was raised. Empirical treatment with Cefotaxime, Clindamycin and cloxacillin started and neonate taken for local debridement. All necrotic tissue was removed including tail of parotid. Over next 5 days serial debridement and wound wash with Hydrogen peroxidase, Betadine, saline and metronidazole was done. The edges of the wound became healthy with no new slough formation and necrotic tissue. An early diagnosis and definitive management with both surgery and antibiotics is the key to a reduce mortality in the neonates. It needs to be followed up with good local wound care.

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A novel Schiff base was synthesized by the condensation of imidazole-2-carboxaldehyde with l-histidine in an equimolar ratio. The prepared Schiff base was characterized by elemental analysis and spectral characterization techniques. It was then complexed with a series of 3-d metal(II) ions like manganese, iron, cobalt, nickel, copper and zinc. The coordination properties, nature of bonding and stability of the complexes were deduced from elemental analysis, IR, UV-vis, 1H NMR, mass, electronic spectra, magnetic, conductivity and thermogravimetric analysis. IR studies support the tridentate behaviour of Schiff base as well as its coordination to the central metal ion through an azomethine nitrogen, deprotonated carboxylic oxygen and imidazole ring nitrogen atoms of histidine. The electronic spectra and magnetic moment data demonstrate that the complexes have an octahedral geometry, except zinc complex, which has a tetrahedral geometry. In vitro antimicrobial activity of the synthesized compounds has been shown to exhibit excellent antibacterial and antifungal activities. The antibacterial property of the prepared Schiff base was further confirmed by conducting a docking study of target proteins involved in the antibacterial mechanism.Communicated by Ramaswamy H. Sarma.

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BACKGROUND: Sequencing Mendelian arrhythmia genes in individuals without an indication for arrhythmia genetic testing can identify carriers of pathogenic or likely pathogenic (P/LP) variants. However, the extent to which these variants are associated with clinically meaningful phenotypes before or after return of variant results is unclear. In addition, the majority of discovered variants are currently classified as variants of uncertain significance, limiting clinical actionability. METHODS: The eMERGE-III study (Electronic Medical Records and Genomics Phase III) is a multicenter prospective cohort that included 21 846 participants without previous indication for cardiac genetic testing. Participants were sequenced for 109 Mendelian disease genes, including 10 linked to arrhythmia syndromes. Variant carriers were assessed with electronic health record-derived phenotypes and follow-up clinical examination. Selected variants of uncertain significance (n=50) were characterized in vitro with automated electrophysiology experiments in HEK293 cells. RESULTS: As previously reported, 3.0% of participants had P/LP variants in the 109 genes. Herein, we report 120 participants (0.6%) with P/LP arrhythmia variants. Compared with noncarriers, arrhythmia P/LP carriers had a significantly higher burden of arrhythmia phenotypes in their electronic health records. Fifty-four participants had variant results returned. Nineteen of these 54 participants had inherited arrhythmia syndrome diagnoses (primarily long-QT syndrome), and 12 of these 19 diagnoses were made only after variant results were returned (0.05%). After in vitro functional evaluation of 50 variants of uncertain significance, we reclassified 11 variants: 3 to likely benign and 8 to P/LP. CONCLUSIONS: Genome sequencing in a large population without indication for arrhythmia genetic testing identified phenotype-positive carriers of variants in congenital arrhythmia syndrome disease genes. As the genomes of large numbers of people are sequenced, the disease risk from rare variants in arrhythmia genes can be assessed by integrating genomic screening, electronic health record phenotypes, and in vitro functional studies. REGISTRATION: URL: https://www. CLINICALTRIALS: gov; Unique identifier; NCT03394859.

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The production of molecular hydrogen by catalyzing water splitting is central to achieving the decarbonization of sustainable fuels and chemical transformations. In this work, a series of structure-making/breaking cations in the electrolyte were investigated as spectator cations in hydrogen evolution and oxidation reactions (HER/HOR) in the pH range of 1 to 14, whose kinetics was found to be altered by up to 2 orders of magnitude by these cations. The exchange current density of HER/HOR was shown to increase with greater structure-making tendency of cations in the order of Cs+ < Rb+ < K+ < Na+ < Li+, which was accompanied by decreasing reorganization energy from the Marcus-Hush-Chidsey formalism and increasing reaction entropy. Invoking the Born model of reorganization energy and reaction entropy, the static dielectric constant of the electrolyte at the electrified interface was found to be significantly lower than that of bulk, decreasing with the structure-making tendency of cations at the negatively charged Pt surface. The physical origin of cation-dependent HER/HOR kinetics can be rationalized by an increase in concentration of cations on the negatively charged Pt surface, altering the interfacial water structure and the H-bonding network, which is supported by classical molecular dynamics simulation and surface-enhanced infrared absorption spectroscopy. This work highlights immense opportunities to control the reaction rates by tuning interfacial structures of cation and solvents.