Heterogeneous Rate Research Articles

Phosphorus limitation on CO2 fertilization effect in tropical forests informed by a coupled biogeochemical model

Tropical forests store more than half of the world's terrestrial carbon (C) pool and account for one-third of global net primary productivity (NPP). Many terrestrial biosphere models (TBMs) estimate increased productivity in tropical forests throughout the 21st century due to CO2 fertilization. However, phosphorus (P) limitations on vegetation photosynthesis and productivity could significantly reduce the CO2 fertilization effect. Here, we used a carbon-nitrogen-phosphorus coupled model (Dynamic Land Ecosystem Model; DLEM-CNP) with heterogeneous maximum carboxylation rates to examine how P limitation has affected C fluxes in tropical forests during 1860–2018. Our model results showed that the inclusion of the P processes enhanced model performance in simulating ecosystem productivity. We further compared the simulations from DLEM-CNP, DLEM-CN, and DLEM-C and the results showed that the inclusion of P processes reduced the CO2 fertilization effect on gross primary production (GPP) by 25% and 45%, and net ecosystem production (NEP) by 28% and 41%, respectively, relative to CN-only and C-only models. From the 1860s to the 2010s, the DLEM-CNP estimated that in tropical forests GPP increased by 17%, plant respiration (Ra) increased by 18%, ecosystem respiration (Rh) increased by 13%, NEP increased by 121% per unit area, respectively. Additionally, factorial experiments with DLEM-CNP showed that the enhanced NPP benefiting from the CO2 fertilization effect had been offset by 135% due to deforestation from the 1860s to the 2010s. Our study highlights the importance of P limitation on the C cycle and the weakened CO2 fertilization effect resulting from P limitation in tropical forests.

Hyperbranched TEMPO-based polymers as catholytes for redox flow battery applications.

Application of redox-active polymers (RAPs) in redox flow batteries (RFBs) can potentially reduce the stack cost through substitution of costly ion-exchange membranes by cheap size-exclusion membranes. However, intermolecular interactions of polymer molecules, i.e., entanglements, particularly in concentrated solutions, result in relatively high electrolyte viscosities. Furthermore, the large size and limited mobility of polymers lead to slow diffusion and more sluggish heterogeneous electron transfer rates compared to quickly diffusing small molecules. Although a number of RAPs with varying electrolyte viscosities have been reported in the literature, the relation between the RAP structure and the hydrodynamic properties has not been thoroughly investigated. Herein, hyperbranched 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO)-based polymers intended for application as low-viscosity catholytes for RFBs are presented and the influence of the structure and the molar mass distribution on the hydrodynamic properties is investigated. A new synthesis approach for TEMPO-based polymers is established based on step-growth polymerization of a TEMPO-containing monomer using an aza-Michael addition followed by a postpolymerization modification to improve solubility in aqueous solutions. The compact structure of hyperbranched polymers was demonstrated using size-exclusion chromatography (SEC) with viscometric detection and the optimum molar mass was found based on the results of viscometric and crossover investigations. The resulting RAP revealed a viscosity of around 21 mPas at a concentration corresponding to around 1 M TEMPO-containing units, according to the calculated mass of the repeating unit, showing potential for high capacity polymer-based catholytes for RFBs. Nevertheless, possible partial deactivation of TEMPO units lowered the active TEMPO concentration of the hyperbranched RAPs. A faster diffusion and higher charge transfer rate were observed for the hyperbranched polymer compared to the previously reported linear polymers. However, in RFB tests, a poor performance was observed, which is attributed to the side reactions of the oxidized TEMPO moieties. Finally, pathways for overcoming the main remaining challenges, i.e., high loss of material during dialysis as an indication of being prone to crossover, the partial deactivation of TEMPO moieties, and the subsequent side reactions under battery conditions, are suggested.

An on-site and portable electrochemical sensing platform based on spinel zinc ferrite nanoparticles for the quality control of paracetamol in pharmaceutical samples.

In this study, crystalline spinel zinc ferrite nanoparticles (ZnFe2O4 NPs) were successfully prepared and proposed as a high-performance electrode material for the construction of an electrochemical sensing platform for the detection of paracetamol (PCM). By modifying a screen-printed carbon electrode (SPE) with ZnFe2O4 NPs, the electrochemical characteristics of the ZnFe2O4/SPE and the electrochemical oxidation of PCM were investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), chronoamperometry (CA), and differential pulse voltammetry (DPV) methods. The calculated electrochemical kinetic parameters from these techniques including electrochemically active surface area (ECSA), peak-to-peak separation (ΔEp), charge transfer resistance (Rct), standard heterogeneous electron-transfer rate constants (k0), electron transfer coefficient (α), catalytic rate constant (kcat), adsorption capacity (Γ), and diffusion coefficient (D) proved that the as-synthesized ZnFe2O4 NPs have rapid electron/mass transfer characteristics, intrinsic electrocatalytic activity, and facilitate the adsorption-diffusion of PCM molecules towards the modified electrode surface. As expected, the ZnFe2O4/SPE offered excellent analytical performance towards sensing of PCM with a detection limit of 0.29 μM, a wide linear range of 0.5-400 μM, and high electrochemical sensitivity of 1.1 μA μM-1 cm-2. Moreover, the proposed ZnFe2O4-based electrochemical nanosensor also exhibited good repeatability, high anti-interference ability, and practical feasibility toward PCM sensing in a pharmaceutical tablet. Based on these observations, the designed electrochemical platform not only provides a high-performance nanosensor for the rapid and highly efficient detection of PCM but also opens a new avenue for routine quality control analysis of pharmaceutical formulations.

Genetic structure and Rickettsia infection rates in Ixodes ovatus and Haemaphysalis flava ticks across different altitudes.

Ixodid ticks, such as Ixodes ovatus and Haemaphysalis flava, are important vectors of tick-borne diseases in Japan, such as Japanese spotted fever caused by Rickettsia japonica. This study describes the Rickettsia infection rates influenced by the population genetic structure of I.ovatus and H. flava along an altitudinal gradient. A total of 346 adult I. ovatus and 243 H. flava were analyzed for the presence of Rickettsia by nested PCR targeting the 17kDA, gltA, rOmpA, and rOmpB genes. The population genetic structure was analyzed utilizing the mitochondrial cytochrome oxidase 1 (cox1) marker. The Rickettsia infection rates were 13.26% in I. ovatus and 6.17% in H. flava. For I. ovatus, the global FST value revealed significant genetic differentiation among the different populations, whereas H. flava showed non-significant genetic differentiation. The cox1 I. ovatus cluster dendrogram showed two cluster groups, while the haplotype network and phylogenetic tree showed three genetic groups. A significant difference was observed in Rickettsia infection rates and mean altitude per group between the two cluster groups and the three genetic groups identified within I. ovatus. No significant differences were found in the mean altitude or Rickettsia infection rates of H. flava. Our results suggest a potential correlation between the low gene flow in I. ovatus populations and the spatially heterogeneous Rickettsia infection rates observed along the altitudinal gradient. This information can be used in understanding the relationship between the tick vector, its pathogen, and environmental factors, such as altitude, and for the control of tick-borne diseases in Japan.

A universal and accurate LPMI method for calculating mismatch in heterogeneous ice nucleation.

The interfacial correlation factor f(m,x), where m refers to the interaction among ice, water and the substrate and x refers to the ratio of the critical nucleation size to the surface topography characteristic size of the substrate, plays a crucial role in the classical theory of heterogeneous ice nucleation as it significantly impacts the energy of nucleation. Generally, a smaller value of f(m,x) indicates a higher propensity for ice nucleation. The degree of structural compatibility between ice and the substrate greatly influences f(m,x), particularly on specific substrates. Several approaches have been proposed to calculate the lattice matching based on this idea, which allows whether a surface is favorable for nucleation to be determined. However, none of these methods adequately correlates the mismatch index with ice growth phenomena. In this paper, we embarked on a new attempt to calculate the mismatch index by combining the lattice parameter and Miller index (LPMI). Droplet freezing experiments have been carried out on α-Al2O3 and silicon surfaces with different Miller indices to verify the rationality of the LPMI method. Furthermore, we validated the LPMI method extensively against other works and further demonstrated its readiness, accuracy and universality for freezing problems. The results consistently show that δd = 2|di - ds|/(di + ds) with interplanar spacing more accurately predicts heterogeneous ice nucleation rates across a wide range of substrates than δ1 = (ai - as)/ai with the lattice parameter of ice and the substrate and is more generally applicable than δ2D = (di - di)/di with the distances between two adjacent and congener atoms on the same plane. We believe that the proposed approach will aid in the selection of substrates for promoting or inhibiting heterogeneous nucleation on a specific substrate.

Electronic structure modification of metal phthalocyanines by a carbon nanotube support for efficient oxygen reduction to hydrogen peroxide.

An active and selective two-electron oxygen reduction reaction (2e- ORR) is required for efficient electrosynthesis of H2O2. This reaction can be promoted by metal phthalocyanines (MPcs), which serve as model catalysts with well-defined structures. MPc molecules have mostly been evaluated on conductive carbon-based substrates, including glassy carbon (GC) and carbon nanotubes (CNTs), yet their influence on the electrocatalytic properties is not well understood. This study demonstrated that the ORR activity per surface area was improved by up to 4-fold with MPc molecules supported on CNTs (MPc/CNTs, M = Co, Mn, and Fe) compared to MPc loaded directly on GC. Ultraviolet photoelectron spectroscopy and density functional theory calculations revealed that the CNTs modified the electronic structure of the MPc molecules to optimize the *OOH binding energy and boost the heterogeneous electron transfer rates. Detailed kinetic analysis enabled multiple reaction pathways to be decoupled to extract the metal-dependent intrinsic 2e-/4e- ORR activities. Finally, MPc/CNT catalysts were employed in an H2O2 electrosynthesis flow cell, which delivered an industrial-scale current density of -200 mA cm-2 and an H2O2 faradaic efficiency of 88.7 ± 0.6% with the CoPc/CNT catalyst in a neutral electrolyte.

Recycled PETg embedded with graphene, multi-walled carbon nanotubes and carbon black for high-performance conductive additive manufacturing feedstock.

The first report of conductive recycled polyethylene terephthalate glycol (rPETg) for additive manufacturing and electrochemical applications is reported herein. Graphene nanoplatelets (GNP), multi-walled carbon nanotubes (MWCNT) and carbon black (CB) were embedded within a recycled feedstock to produce a filament with lower resistance than commercially available conductive polylactic acid (PLA). In addition to electrical conductivity, the rPETg was able to hold >10 wt% more conductive filler without the use of a plasticiser, showed enhanced temperature stability, had a higher modulus, improved chemical resistance, lowered levels of solution ingress, and could be sterilised in ethanol. Using a mix of carbon materials CB/MWCNT/GNP (25/2.5/2.5 wt%) the electrochemical performance of the rPETg filament was significantly enhanced, providing a heterogenous electrochemical rate constant, k0, equating to 0.88 (±0.01) × 10-3 cm s-1 compared to 0.46 (±0.02) × 10-3 cm s-1 for commercial conductive PLA. This work presents a paradigm shift within the use of additive manufacturing and electrochemistry, allowing the production of electrodes with enhanced electrical, chemical and mechanical properties, whilst improving the sustainability of the production through the use of recycled feedstock.

Laser-induced fibers and copper phthalocyanine modified laser-induced graphene electrodes for sensitive and selective electrochemical detection of nitrite.

We have recently reported laser-induced fibers (LIF) as a promising nanomaterial that possesses good electrochemical activity and are easily manufacturable. In this paper, for the first time, the application of LIF as functionalization materials on laser-induced graphene (LIG) electrodes for the detection of nitrate is demonstrated. The as-fabricated LIF surfaces on Kapton were extracted by ultrasonication as a dispersion and were used to modify the surface of the LIG electrode. An enhancement in active surface area from 0.669 cm2 for bare LIG to 0.83 cm2 for LIF-modified LIG was observed. Similarly, the heterogeneous electron transfer rate increased from 0.190 to 0.346 cm s-1 for LIF/LIG electrodes. The electrochemical detection of nitrite was achieved by modifying the LIG with a nanocomposite of LIF and copper phthalocyanine (CuPc). The presence of CuPc provided the desired catalytic activity towards the oxidation of nitrite, and the LIF enhanced the electron transfer to the electrode. Such a synergetic combination of the LIF embedded with CuPc enabled reaching a low limit of detection (LoD) of 0.12 μM, a large linear range from 10 to 10 000 μM and good selectivity in the presence of potential interferants. The sensor had a long shelf life of 30 days and good analytical capability to detect nitrite in mineral, tap, and groundwater. The potential of LIF is largely unexplored and the findings reported here on the fibers would open manifold opportunities for realizing novel applications.

Anti-tumor effect of pH-sensitive drug-loaded nanoparticles optimized via an integrated computational/experimental approach.

The acidic pH of tumor tissue has been used to trigger drug release from nanoparticles. However, dynamic interactions between tumor pH and vascularity present challenges to optimize therapy to particular microenvironment conditions. Despite recent development of pH-sensitive nanomaterials that can accurately quantify drug release from nanoparticles, tailoring release to maximize tumor response remains elusive. This study hypothesizes that a computational modeling-based platform that simulates the heterogeneously vascularized tumor microenvironment can enable evaluation of the complex intra-tumoral dynamics involving nanoparticle transport and pH-dependent drug release, and predict optimal nanoparticle parameters to maximize the response. To this end, SPNCD nanoparticles comprising superparamagnetic cores of iron oxide (Fe3O4) and a poly(lactide-co-glycolide acid) shell loaded with doxorubicin (DOX) were fabricated. Drug release was measured in vitro as a function of pH. A 2D model of vascularized tumor growth was calibrated to experimental data and used to evaluate SPNCD effect as a function of drug release rate and tissue vascular heterogeneity. Simulations show that pH-dependent drug release from SPNCD delays tumor regrowth more than DOX alone across all levels of vascular heterogeneity, and that SPNCD significantly inhibit tumor radius over time compared to systemic DOX. The minimum tumor radius forecast by the model was comparable to previous in vivo SPNCD inhibition data. Sensitivity analyses of the SPNCD pH-dependent drug release rate indicate that slower rates are more inhibitory than faster rates. We conclude that an integrated computational and experimental approach enables tailoring drug release by pH-responsive nanomaterials to maximize the tumor response.

Improved solubility of titanium-doped polyoxovanadate charge carriers for symmetric non-aqueous redox flow batteries.

Non-aqueous redox flow batteries constitute a promising solution for grid-scale energy storage due to the ability to achieve larger cell voltages than can be readily accessed in water. However, their widespread application is limited by low solubility of the electroactive species in organic solvents. In this work, we demonstrate that organic functionalization of titanium-substituted polyoxovanadate-alkoxide clusters increases the solubility of these assemblies over that of their homoleptic congeners by a factor of >10 in acetonitrile. Cyclic voltammetry, chronoamperometry, and charge-discharge cycling experiments are reported, assessing the electrochemical properties of these clusters relevant to their ability to serve as multielectron charge carriers for energy storage. The kinetic implications of ligand variation are assessed, demonstrating the role of ligand structure on the diffusivity and heterogeneous rates of electron transfer in mixed-metal charge carriers. Our results offer new insights into the impact of structural modifications on the physicochemical properties of these assemblies.

Fast discharging mitigates cathode-electrolyte interface degradation of LiNi0.6Mn0.2Co0.2O2 in rechargeable lithium batteries

The rapid deterioration of lithium-ion batteries in fast-charging and discharging conditions poses a major challenge for future mobility technologies. Accelerated failure is attributed to the non-equilibrium de/lithiation reaction at inter- and intra-particle levels in electrodes induced by high current densities. However, the correlation between the reaction heterogeneity and degradation rate remains elusive. Here, we unambiguously decouple the effects of fast charging and discharging on battery degradation by applying asymmetric charging–discharging protocols. Our findings reveal that fast charging stimulates the electrolyte decomposition and surface reconstruction and, surprisingly, fast discharging mitigates these detrimental effects. The improved cyclability originates from the kinetically lowered depth of discharge (DOD) upon fast discharging, enabling a homogeneous electrochemical reaction by evading the slow-kinetics state-of-charge regime. Proving the beneficial effect of limiting DOD, we demonstrate a protocol that effectively suppresses degradation under fast charging conditions, resulting in negligible capacity decay while delivering an accumulated capacity of 30 Ah g−1. In contrast, conventional protocols show drastic capacity decay (13.8% retention). This study establishes a causal coupling between cathode degradation, reaction heterogeneity, and current density and direction at multiple length scales, providing valuable guidance for designing advanced battery cycling protocols that promote stable long-term battery operation, particularly under fast-charging conditions.

The effect of gold nanostructure morphology on label-free electrochemical immunosensor design

In this research, various electrodeposition techniques were used to form gold nanostructures (AuNSs) on the surface of graphite rod electrode (GE). Three distinct AuNS morphologies on GE have been achieved based on the composition of electrodeposition solution. The use of H2SO4 as a supporting electrolyte resulted in the formation of smaller but more numerous AuNSI with a modified electrode’s electroactive surface area (EASA) of 0.213 cm2. Exchanging the supporting electrolyte to KNO3 and increasing HAuCl4 concentration facilitated the formation of bigger AuNSII particles with electrode EASA of 0.116 cm2. Finally, a partial coverage of GE by branched gold nanostructures (AuNSIII) was achieved with an estimated EASA of 0.110 cm2, when the HAuCl4 and KNO3 concentrations were increased. Estimated values of heterogeneous electron transfer rate constant did not depend on AuNS morphology. Electrode modified with AuNSI exhibited the highest bovine serum albumin (BSA) immobilization efficiency and the highest relative response for the detection of specific polyclonal antibodies against BSA (p-anti-BSA) compared to other modified electrodes. The limit of p-anti-BSA detection in PBS buffer was calculated as 0.63 nM, while in blood serum it was 0.71 nM. Linear ranges were from 1 to 7 nM and from 1 to 5 nM, respectively.

Design Space Exploration of DVFS on On-Chip Hybrid Communication Networks

Multi-Processor Systems-on-Chip (MPSoCs) have been established as the standard platform for high-performance applications in the semiconductor industry. With an increasing number of Processing Elements (PEs) in a single die, communication scalability is one of the foremost concerns. Networks-on-Chip (NoCs) has already shown to be an alternative to provide scalability, but relies on homogeneous communication fashion which cannot be ideal to heterogeneous communication demand of current embedded devices. Hybrid communication structures can mitigate such issues by merging different communication structures that can better accommodate heterogeneous communication rates. In this work, an Hybrid Communication Infrastructure is proposed by merging fully- partially- and peer to peer connected fabrics providing a wide range of communication bandwidth. In addition, we coupled to the hybrid fabric, a multi-grained DVFS approach that dynamically adapts voltage and frequency of the structures considering the application's performance needs. Results shows that the Hybrid structure achieves up to 22% power savings and occupied 42% less chip area than a NoC with the same number of PEs. Experiments with relevant video encoding applications show power savings of up to 70% over a homogeneous NoC, with no significant throughput losses, both coupled to the proposed DVFS approach.

Cytochrome c oxidase deficiency detection in human fibroblasts using scanning electrochemical microscopy.

Cytochrome c oxidase deficiency (COXD) is an inherited disorder characterized by the absence or mutation in the genes encoding for the cytochrome c oxidase protein (COX). COX deficiency results in severe muscle weakness, heart, liver, and kidney disorders, as well as brain damage in infants and adolescents, leading to death in many cases. With no cure for this disorder, finding an efficient, inexpensive, and early means of diagnosis is essential to minimize symptoms and long-term disabilities. Furthermore, muscle biopsy, the traditional detection method, is invasive, expensive, and time-consuming. This study demonstrates the applicability of scanning electrochemical microscopy to quantify COX activity in living human fibroblast cells. Taking advantage of the interaction between the redox mediator N, N, N', N'-tetramethyl-para-phenylene-diamine, and COX, the enzymatic activity was successfully quantified by monitoring current changes using a platinum microelectrode and determining the apparent heterogeneous rate constant k0 using numerical modeling. This study provides a foundation for developing a diagnostic method for detecting COXD in infants, which has the potential to increase treatment effectiveness and improve the quality of life of affected individuals.

Freedivers harvest thousands of sea turtles a year in the Solomon Islands

Abstract Sea turtles are harvested in many small‐scale fisheries (SSFs), but few nations have quantified the impacts that SSFs are having on their sea turtle stocks. This study provides the first assessment on the catch composition, national harvest rates, and long‐term trends in sea turtle catches in the Solomon Islands SSFs. Between October 2016 and May 2018, 10 community monitors located in eight of the nine provinces of the Solomon Islands were trained and employed to work alongside fishers in their respective communities to document, photograph, and georeference the reefs where sea turtles were harvested. Local ecological knowledge (LEK) surveys were then conducted with 32 experienced fishers to infer whether the harvest rates of sea turtles had changed in recent decades. Community monitors recorded information on 1,132 sea turtles that were harvested on 529 fishing trips: 1,119 sea turtles were identified to species level, with harvests consisting of 73.3% (n = 818) green sea turtles (Chelonia mydas), 25.7% hawksbill sea turtles (n = 291) (Eretmochelys imbricata), and 0.9% (n = 10) olive ridley sea turtles (Lepidochelys olivacea). The great majority (92.6%) of sea turtles were captured by night‐time and daytime freedivers who use masks, snorkels, fins, hooks, spears, and underwater flashlights to target a wide range of fauna that inhabit coral reefs. A methodology that accounts for spatial heterogeneity in sea turtle catch rates was used to estimate that the SSFs of the Solomon Islands harvested 11,184 sea turtles per year, with a 95% confidence interval of 5,862–23,717 sea turtles. Experienced freedivers reported a 4.9‐fold decline in sea turtle harvest rates over the past 30 years, indicating that the sea turtle stocks of the Solomon Islands are being overfished. The results and recommendations from this study were integrated into the Solomon Islands National Plan of Action for Marine Turtles 2023–2027.

Genomics in Clinical trials for Breast Cancer.

Breast cancer (B.C.) still has increasing incidences and mortality rates globally. It is known that B.C. and other cancers have a very high rate of genetic heterogeneity and genomic mutations. Traditional oncology approaches have not been able to provide a lasting solution. Targeted therapeutics have been instrumental in handling the complexity and resistance associated with B.C. However, the progress of genomic technology has transformed our understanding of the genetic landscape of breast cancer, opening new avenues for improved anti-cancer therapeutics. Genomics is critical in developing tailored therapeutics and identifying patients most benefit from these treatments. The next generation of breast cancer clinical trials has incorporated next-generation sequencing technologies into the process, and we have seen benefits. These innovations have led to the approval of better-targeted therapies for patients with breast cancer. Genomics has a role to play in clinical trials, including genomic tests that have been approved, patient selection and prediction of therapeutic response. Multiple clinical trials in breast cancer have been done and are still ongoing, which have applied genomics technology. Precision medicine can be achieved in breast cancer therapy with increased efforts and advanced genomic studies in this domain. Genomics studies assist with patient outcomes improvement and oncology advancement by providing a deeper understanding of the biology behind breast cancer. This article will examine the present state of genomics in breast cancer clinical trials.

Reaction characteristics of homogeneous and heterogenous reactions for glucose gasification in supercritical water using ruthenium catalyst supported on carbon nanotube

In this study, a spherical, Ru-based catalyst with a Carbon nanotube (CNT) support was used in a continuous-flow system, where homogeneous and heterogeneous reactions occurred simultaneously. Therefore, determining the homogeneous and heterogeneous reaction rates is important. Glucose (5 and 10) wt%, a typical model biomass compound, was chosen as the feedstock, and the reaction temperature was set at (500 and 600) ℃. The weight hourly space velocity was changed (40, 80, or 160) h−1 by maintaining the catalyst loading at 0.15 g and altering the flow rate (2, 4, or 8) mL/min. A reaction model where homogeneous and heterogeneous reactions proceed in parallel was developed, and the reaction rates were determined. The homogeneous reaction rate constants were (0.00968 and 0.0194) /s for (500 and 600) ℃, respectively, and the heterogeneous ones for Ru-based catalyst with a CNT support were (0.0137 and 0.0420) m3/(kg s) for (500 and 600) ℃, respectively.

Reproducibility in Management Science

With the help of more than 700 reviewers, we assess the reproducibility of nearly 500 articles published in the journal Management Science before and after the introduction of a new Data and Code Disclosure policy in 2019. When considering only articles for which data accessibility and hardware and software requirements were not an obstacle for reviewers, the results of more than 95% of articles under the new disclosure policy could be fully or largely computationally reproduced. However, for 29% of articles, at least part of the data set was not accessible to the reviewer. Considering all articles in our sample reduces the share of reproduced articles to 68%. These figures represent a significant increase compared with the period before the introduction of the disclosure policy, where only 12% of articles voluntarily provided replication materials, of which 55% could be (largely) reproduced. Substantial heterogeneity in reproducibility rates across different fields is mainly driven by differences in data set accessibility. Other reasons for unsuccessful reproduction attempts include missing code, unresolvable code errors, weak or missing documentation, and software and hardware requirements and code complexity. Our findings highlight the importance of journal code and data disclosure policies and suggest potential avenues for enhancing their effectiveness. This paper was accepted by David Simchi-Levi, behavioral economics and decision analysis–fast track. Supplemental Material: The online appendices and data are available at https://doi.org/10.1287/mnsc.2023.03556 .

(Invited) The Effect of Surfactants on Vanadium Electrochemistry in Porous Carbon Electrodes

We present a study of vanadium electrochemistry in porous electrodes with and without sodium dodecyl sulfate (SDS) additives present. Carbon paper and felt electrodes are compared. Carbon felt electrodes are the de facto standard in flow batteries. There are significant differences in the electronic conductivity of these media. The carbon paper has a much higher conductivity than the felt, which has an electronic conductivity similar to the ionic conductivity of the electrolytes used. The latter fact motivates an extension of available theory for polarization curve fitting to explicitly include both electronic and ionic contributions in the porous electrode. We demonstrate agreement between our model and an existing model evaluated at the limit where electrode conductivity is significantly greater than electrolyte conductivity. Our model uses the product of the electrode surface area per volume ratio and the heterogeneous electron transfer rate constant, and the Damköhler number as fitting parameters for carbon paper and felt electrodes. We discuss the effect of SDS additives on kinetics in the context of the cation hydration shell for the vanadium ions. To this point, we apply Marcus-Hush-Chidsey formalism to our porous electrode model to quantify reorganization energies obtained through polarization curve fitting. This work was supported as part of the Breakthrough Electrolytes for Energy Storage (BEES2), an Energy Frontier Research Center funded by the United States. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0019409.

Electrochemical Evaluation of Manganese Electrolytes for Redox Flow Batteries

Redox flow batteries (RFBs) are promising candidates for long-duration energy storage mainly due to the lower cost of improving the energy density compared to lithium-ion batteries. However, the full sustainability of RFBs has not been achieved yet, and there is a lot of room for further improvement. One of the main parameters showing a strong influence on the sustainability of RFBs is redox active materials. In this work, manganese was selected for electrochemical evaluation as it fulfills the sustainability requirements. Manganese is a non-toxic, low-cost and abundant material with sufficient aqueous solubility[1]. Moreover, the standard potential of manganese (1.51 V) is higher than that of vanadium (1.26 V).For electrochemical parameters, we have, through cyclic voltammetry (CVs) and polarization curves, estimated the diffusion coefficient (D0 ) and heterogeneous standard electron transfer rate (k 0) of manganese in an acidic electrolyte in the presence of titanium as an additive. In order to investigate the performance of an RFB system using a manganese electrolyte, a hybrid system was designed that uses hydrogen gas on the negative side and an acidic manganese electrolyte the positive side. We have studied the resistance behavior of the hybrid RFB through electrochemical impedance spectroscopy at different states of charge. From EIS data, cell ohmic resistance, and a general idea of the different processes taking place at different state of charge were obtained. Moreover, we studied the performance of the hybrid RFB during 70 cycles, obtaining an average coulombic efficiency of 98.1%, voltage efficiency of 77.8% and capacity retention of 97.7%. Carney, J.R., B.R. Dillon, and S.P. Thomas, Recent Advances of Manganese Catalysis for Organic Synthesis. European Journal of Organic Chemistry, 2016. 2016(23): p. 3912-3929.