Poor Transport Research Articles

High-Density CuBi2O4 Photocathodes Using Well-Textured Buffer Layers and Their Unassisted Solar Hydrogen Production Performances.

Solar hydrogen production using photoelectrochemical (PEC) cells requires the selection of cost-effective materials with high photoactivity and durability. CuBi2O4 photocathodes possess an appropriate bandgap for efficient hydrogen production. However, their performance is limited by poor charge transport and interface voids formed due to the porous structure during annealing, which complicates the deposition of passivation overlayers. To address this, effective suppression of the porous structure in CuBi2O4 is essential. Here, the study proposes the strategic use of an Sb-Cu2O buffer layer with a uniform (111) crystal orientation prior to the electrodeposition of Cu-Bi-O. This buffer layer facilitates 2D film growth during electrodeposition, enhancing Cu supply via out-diffusion from the buffer during annealing. Moreover, the uniform orientation of the buffer layer promotes the crystallization of CuBi2O4, significantly improving charge transport efficiency. By incorporating an Al-ZnO/TiO2 overlayer, the study achieves a photocurrent of 2.56 mA cm-2 at 0 VRHE and an onset potential of 1.04 VRHE, with excellent stability exceeding 60 hours. In a glycerol oxidation reaction coupled with hydrogen production, an unassisted PEC cell with a BiVO4 photoanode demonstrates the highest H2 production (750.5 µmol cm-2) among Cu-based ternary oxides, with 97% Faradaic efficiency over 20 hours while producing DHA, and formic acid.

Exploring factors behind patient non-adherence to intravitreal anti-VEGF injections in macular diseases.

In recent years, intravitreal injections (IVT) of vascular endothelial growth factor (VEGF) inhibitors have become the standard of care for several macular disorders. Frequently, the therapeutic course requires numerous injections, posing a burden on patients. Non-adherence to treatment may result in reduced visual outcomes, therefore understanding and addressing the underlying causes is imperative. A cross-sectional study of patients who missed their scheduled appointment for anti-VEGF IVT as part of the routine management of their macular disease at a single tertiary center between November 2020 and February 2021. A telephone survey was conducted and patient medical charts were reviewed for ophthalmological data. A total of 100/556 (18%) patients who failed to attend their scheduled anti-VEGF IVT appointments were documented. Among these subjects, the average age was 66 (SD ±14) years with a nearly equal gender distribution of 49:51 F:M ratio. Reported no-show reasons included concurrent illness (39%), administrative issues such as missing financial coverage forms or scheduling problems (28%), and lack of motivation (11%). Additionally, 73% of patients who missed appointments expressed a need for accompaniment, and 74% resided outside the hospital city. Study results highlight modifiable factors contributing to no-shows to anti-VEGF IVT, such as poor transportation access, complicated administrative processes, and difficulty rescheduling missed appointments. Understanding potential obstacles to anti-VEGF IVT therapy, particularly those that are preventable, can enhance adherence and potentially improve the clinical outcome.

Rapid detection assays for Bacillus anthracis, Yersinia pestis, and Brucella spp. via triplex-recombinase polymerase amplification.

Bacillus anthracis (B. anthracis), Yersinia pestis (Y. pestis), and Brucella spp. are zoonotic bacteria that cause anthrax, plague, and brucellosis, respectively. Outbreaks typically occur in remote regions with poor transportation and limited laboratory testing. Therefore, a simple, sensitive, multiplex nucleic acid detection method is essential for effective disease management and control. Primers and probes for the three pathogens were designed to reduce interference from related strains. Three recombinase polymerase amplification (RPA) reactions were conducted at 39°C for 10min to produce species-specific fluorescence signals for the three pathogens. These were integrated, and conditions were optimized for rapid, sensitive triplex-RPA assays without cross-reactivity. A triplex-RPA reaction with lateral flow dipsticks (LFDs) was developed and applied to blood samples, newly isolated strains, and simulated samples. Highly sensitive and specific primers and probes were developed, achieving a maximum sensitivity of 1 copy/µL in single-reaction RPA. The optimized triplex RPA detection technique, combined with fluorescence, effectively identified B. anthracis, Y. pestis, and Brucella spp. within 20min, whereas LFDs achieved detection in 10min. The assay also performed comparably to conventional polymerase chain reaction techniques when tested on blood samples, newly isolated strains, and simulated samples. This study offers reliable methods for detecting B. anthracis, Y. pestis, and Brucella spp. in rural hospitals and public health initiatives.

Exploring smallholder farmers’ access and participation in the Home Grown School Feeding Programme in selected counties of Kenya

IntroductionSmallholder farmers (SHFs) produce 80% of the total agricultural output in Kenya. The Home Grown School Feeding Programme (HGSFP) was designed to address short-term hunger among primary school children from food-insecure households, enhancing access to primary education while providing a market to SHFs through local procurement of food for schools. This study investigated SHF access and participation in the HGSFP market and the uptake of a mobile phone platform (MPP) in HGSFP procurement in Tharaka Nithi, Kitui and Kilifi Counties of Kenya.MethodologyDescriptive cross-sectional study design was utilized and data were collected from SHFs, school teachers and farmer-based organizations (FBOs) within the schools’ locality using semi-structured questionnaires. A total of 378 SHFs, 92 FBOs and 70 school teachers were interviewed for the study. Data were analyzed using Stata version 16.ResultsThe study revealed that SHFs (22.8%) and FBOs (37.5%) gained access to HGSFP market and sold produce of maize (92.9%) and beans (91.4%). The main channel used by SHFs to sell produce to schools was through the FBOs (61.6%) amidst challenges of lack of surplus to sell (53.2%), low prices (50.9%) and poor transport infrastructure (23.6%). HGSFP schools purchased most of their food requirements from traders/brokers through manual tendering (65%). The uptake of the MPP for procurement of food by HGSFP schools and FBOs was embraced and promising and was rated as faster to use (76.8%) and more transparent in HGSFP procurement (44.6%).ConclusionThe study concluded that local procurement opportunities through FBOs were underutilized. We recommend more capacity-building support for SHFs and FBOs to increase their production and give them better opportunities to be key participants in the HGSFP market and other structured markets. The MPP should be adopted for the procurement of food for school meals for transparency and accountability. To maximize its benefits, it should be inclusive of all market players, especially traders/brokers and sufficient training should be provided to all stakeholders to participate fully in the HGSFP market.

Ex nihilo urbanization in Nigeria: Colonial legacies, privatization, and foreign actors

ABSTRACT Over the past 2 decades, Nigeria has become a hotspot for the creation of new cities, with a dozen currently underway. While new cities in Nigeria are promoted by their developers as necessary for addressing the urban challenges plaguing cities, including overcrowding, housing deficits, a lack of amenities, and poor transportation infrastructure, we suggest that new cities in Nigeria are products of neoliberal urban policies and that they prioritize luxury and exclusivity. The current new city boom in Nigeria tracks with the global proliferation of projects of similar scale and ambition, but our research highlights that building ex nihilo new cities has a long history in Nigeria dating back to British colonialism. This paper identifies 39 ex nihilo urban mega-developments carried out in Nigeria since the British colonial era and examines their strategic locations and rationales, the key actors involved, and the urban practices guiding their creation in three distinct eras—colonial, post-independence, and contemporary—in order to understand the continuities and differences in new city development over time.

Accessibility of psychological treatments for chronic pain in low socioeconomic settings.

Chronic pain is a highly prevalent condition globally. Low-socioeonomic (SES) populations tend to have higher prevalence rates and worsened pain outcomes. Although psychological interventions for chronic pain are considered an integral aspect of chronic pain treatment, psychological treatments are often not accessible for individuals with low-SES due to barriers such as poor insurance coverage, transportation and financial issues, lack of access to pain-trained providers, and educational resources with inappropriately high literacy levels. Within recent years, there have been some advances in methods to increase accessability. In this paper, we review recent methods to enhance accessability of psychological treatments for chronic pain in low-SES settings and suggest areas for future growth.

Stable structure and oxygen-rich vacancy assist NH4V4O10 to become a high-performance aqueous zinc-ion battery cathode material

Ammonium vanadate (NH4V4O10) is an emerging cathode material for aqueous zinc-ion batteries (AZIBs), gaining recognition for V element multivalent and budget. However, Zn2+ exhibit robust coulombic bonds with the lattice structure, poor ion transport and cycling stability, and narrow layer spacing limit its further application. In this study, we prepared an efficient cathode designed for AZIBs by inserting ascorbic acid (AA) into the interlayer of NH4V4O10 (AANVO). The insertion of AA increases the distance between layers and enhances the stability of the material's structure, provided a large interlayer channel for the diffusion of Zn2+ and successfully partially replaced NH4+ in NH4V4O10, alleviating the irreversible deamination reaction. Furthermore, the doping of AA reduces the crystallinity of NVO, increases the oxygen vacancies, and accelerates the ion and charge transfer kinetics, resulting in excellent electrochemical properties. The findings reveal that AANVO exhibits a remarkable charge capacity of 638 mAh g-1 at 0.1Ag-1, and it maintains 86.6% of this capacity after 1000 cycles when subjected to 10Ag-1.

Hyper-Thick Electrodes for Lithium-Ion Batteries Enabled by Micro-Electric-Field Process.

Increasing electrode thickness is a key strategy to boost energy density in lithium-ion batteries (LIBs), which is essential for electric vehicles and energy storage applications. However, thick electrodes face significant challenges, including poor ion transport, long diffusion paths, and mechanical instability, all of which degrade battery performance. To overcome these barriers, a novel micro-electric-field (μ-EF) process is introduced that enhances particle alignment during fabrication with reduced distance between anode and cathode. This process produces hyper-thick (≈700µm) electrodes with low tortuosity and improved ion diffusion. The μ-EF electrodes achieve high areal capacities (≈8mAhcm-2), while maintaining power density and long cycle life. The electrodes show stable performance under high C-rate cycling and retain structural integrity after 1000 cycles at 2 C. By offering a scalable solution to the challenges of thick electrode fabrication, the μ-EF process represents a significant advancement for high-capacity LIBs in electric vehicles and energy storage systems.

Tackling Cardiovascular Care Deserts in Romania: Expanding Population Access in Underserved Areas

Background: Cardiovascular deserts are areas that lack medical facilities, specialists and equipment to effectively diagnose, treat and manage cardiovascular diseases (CVDs). Romania registers the highest incidence and the highest mortality due to CVDs in Europe. Population ageing is a significant concern, as it increases the risk of CVDs and the demand for specialised care. Although almost 50% of Romanians still live in rural areas, most medical resources are concentrated in a few large cities, leaving large parts of the country underserved. Methods: This study used the Application Programming Interface (API) Matrix service from Google Maps and open data sources to identify cardiovascular (CV) deserts. Results: This research indicates that over 64% of the Romanian population resides in areas lacking CV care, having to travel more than 60 km and over 30 min to reach the nearest facility that offers specialised treatment. Moreover, 14% live in areas affected by a high degree of cardiovascular desertification. These areas are primarily located in northeastern, southern and western Romania. They experience higher mortality rates from CVDs and an ageing population, along with a shortage of general physicians and a scarcity of cardiologists. Conclusions: The identified cardiovascular deserts in this study overlap mountainous regions, the Danube Delta and remote rural areas with poor transportation infrastructure. Implementing telemedicine or mobile healthcare services, involving community healthcare workers and policy support could be solutions to expand access to specialised care in cardiovascular deserts.

The Role of Pharmacogenetic Testing in Overcoming Pseudoresistance and Hyperprolactinemia in a Patient with Schizophrenia (Case Report)

Schizophrenia is a chronic mental disorder. It is treated with antipsychotics, which have a high risk of adverse drug reactions. Approximately 20-30% of patients with schizophrenia remain resistant to psychopharmacotherapy. Determining the individual predisposition to the response to antipsychotics and antipsychotic-induced adverse drug reactions development is possible using pharmacogenetic testing. Purpose is to present the role of pharmacogenetic testing in optimizing antipsychotic therapy. Materials and methods: The peripheral blood of patients was genotyping using real-time polymerase chain reaction. Results: This case report is about a 30- year-old female patient with paranoid schizophrenia, which had a long history of low effectiveness and poor tolerability of antipsychotics. The treatment was complicated by the pituitary microadenoma presence. According to the PGx results, the patient has a “poor transporter” phenotype, which also explains the high risk adverse drug reactions developing and therapeutic resistance while taking P- glycoprotein substrates antipsychotics. For the treatment, the antipsychotic brexpiprazole was selected, which did not have the P-glycoprotein substrate properties. It made possible to achieve paranoid schizophrenia remission and hyperprolactinemia correction. Conclusion: This case report demonstrates that wider implementation of pharmacogenetic testing into real clinical practice could help significantly improve the efficiency and safety of antipsychotic therapy.

Effective Dopants Pb and Pb‐SiW12 to Enhance Sb2S3‐Based Photodetector Performance

AbstractSb2S3 has excellent photovoltaic properties, but the performance of its photovoltaic devices still needs to be improved. The main issues hindering its photovoltaic performance are the poor carrier transport ability and the significant charge recombination. Doping strategies play a key role in addressing these issues. This study investigates the effect of Pb(CH3COO)2 (Pb) and [Pb(DMF)7]2[SiW12O40] 2DMF (Pb‐SiW12) doping on the photovoltaic properties of Sb2S3 thin films. It is found that the intensity of diffraction peaks on the (130) crystal plane of Pb‐doped Sb2S3 and the (221) crystal plane of Pb‐SiW12@Sb2S3 is increased, which enhances the crystallinity of the films. Meanwhile, Pb and Pb‐SiW12 doping narrow the bandgap (1.69 eV) of Sb2S3 to 1.65 eV and 1.62 eV. Electrochemical tests show that the carrier concentration and carrier lifetime are increased. The Pb‐doped Sb2S3 photodetector photocurrent of 14 μA, 7 times higher than the 2 μA pristine Sb2S3 photodetector. It exhibits a responsivity of 13.9 mA/W and detectivity of 1.2×1011 Jones. The Pb‐SiW12@Sb2S3 photodetector photocurrent is 11 μA. Pb‐SiW12 can immobilize Pb while reducing the amount of Pb. The methodology in this work provides a way to improve the performance of Sb2S3 thin‐film photodetectors.

Late Harvest: Freezing Temperatures Reduce the Root Yield and Sugar Content of Beta vulgaris L.

ABSTRACTSugar beet (Beta vulgaris L.) is the main source of white sugar in northern China, and an optimal harvesting time is key for maximising its yield and sugar content. The goal of this study was to investigate the effect of gradually extending harvest times on the growth, physiological characteristics, yield and sucrose accumulation in sugar beet and identify the optimal harvesting time. We conducted a 3‐year experiment across different harvesting times from 23 Sep to 28 Oct (harvest every 7 days) to examine the effects of different magnitudes of temperature reduction. The yield and sugar content were the highest in time III (the daily mean/minimum temperature: 9.5°C/5°C) in 2020, time III (the daily mean/minimum temperature: 8.2°C/2°C) and IV (the daily mean/minimum temperature: 10.1°C/2°C) in 2021 and time IV (the daily mean/minimum temperature: 10.5°C/5°C) and V (the daily mean/minimum temperature: 7°C/−1°C) in 2022. The yield and sugar content were low at an early harvest, as the biomass and sucrose accumulation process was not complete. However, the decrease in temperature (daily minimum temperature below 0°C) during late harvest leads to a decrease in the yield and sugar content because of the decreased sucrose accumulation of source leaves, increased sucrose decomposition and the poor transport capacity of phloem in the stem. Therefore, the optimal harvesting time for sugar beet in northern China depends on temperature conditions. It is optimal when (1) the daily minimum temperature gradually decreases to 0°C but not lower than 0°C and when (2) the daily mean temperature is approximately 10°C. This work will help sugar beet producers harvest high‐quality crops and reduce unnecessary losses in northern China.

Tailoring high-performance bipolar membrane for durable pure water electrolysis

Bipolar membrane electrolyzers present an attractive scenario for concurrently optimizing the pH environment required for paired electrode reactions. However, the practicalization of bipolar membranes for water electrolysis has been hindered by their sluggish water dissociation kinetics, poor mass transport, and insufficient interface durability. This study starts with numerical simulations and discloses the limiting factors of monopolar membrane layer engineering. On this foundation, we tailor flexible bipolar membranes (10 ∼ 40 µm) comprising anion and cation exchange layers with an identical poly(terphenyl alkylene) polymeric skeleton. Rapid mass transfer properties and high compatibility of the monopolar membrane layers endow the bipolar membrane with appreciable water dissociation efficiency and long-term stability. Incorporating the bipolar membrane into a flow-cell electrolyzer enables an ampere-level pure water electrolysis with a total voltage of 2.68 V at 1000 mA cm–2, increasing the energy efficiency to twice that of the state-of-the-art commercial BPM. Furthermore, the bipolar membrane realizes a durability of 1000 h at high current densities of 300 ∼ 500 mA cm–2 with negligible performance decay.

Utilizing Ionic Liquid Mixtures to Modify Lithium Solvation Chemistry and Electrolyte Properties

Ionic liquids are appealing as electrolytes because of their wide electrochemical windows, moderate conductivities, minimal flammability and ability to tune the structure-property relationships. Shortcomings with the use of ionic liquids in lithium-based batteries are due to poor lithium ion transport, lack of formation of a stable solid electrolyte interphase (SEI) and limited lower temperature operations. To overcome the shortcomings, ionic liquids can be mixed with co-solvents or additives. SEI formers, co-solvents for lowering melting points and increasing conductivities, and agents to modify the interactions with lithium can all be introduced to the ionic liquid electrolytes. In the work to be presented here, the strategy of mixing solvate ionic liquids (Li(G4)TFSI) with task-specific pyrrolidinum-based ionic liquids that have short polyether side chains will be presented. Li(G4)TFSI is a solvate ionic liquid with an equimolar ratio of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and tetraethylene glycol dimethyl ether (G4). Li(G4)TFSI with an oxygen-to-lithium ratio of 5 ([O]/[Li+]=5), has a high lithium concentration and improved low temperature liquid range compared to traditional ionic liquids. By adding the task-specific ionic liquids with solvate ionic liquid analogous side chains, the properties of the electrolyte can further be tuned while aiming to keep the anion from solvating the Li ion which hinders its transport. The length of the polyether groups on the ionic liquid were varied to have constant ratios of ionic liquid:LiTFSI:G4 or to maintain a constant [O]/[Li+] ratio. The influence of the anion utilized with the ionic liquid was also investigated. The physical and electrochemical characteristics of the ionic liquid mixtures were evaluated to better understand how key properties and solvating power affect reversible lithium deposition and stripping across a range of temperatures. Through the use of ionic liquid-based mixtures, many of the desirable properties of the ionic liquids can be retained while the undesired properties of the ionic liquids can be mitigated, making for more favorable electrolytes.

Monolithic Lead Halide Perovskite Based Photoanode with 9.16% Applied Bias Photon-to-Current Efficiency

The quest for sustainable hydrogen production through solar energy conversion has directed attention towards photoelectrochemical (PEC) cell water splitting, a promising avenue for hydrogen (H₂) generation. Traditional metal-oxide-based photoelectrodes such as TiO2 and WO3, despite their extensive study, fail to absorb visible light effectively and exhibit poor charge transport properties. In contrast, lead halide perovskites (LHPs) emerge as a superior alternative, endowed with exceptional optoelectronic properties that enhance the solar spectrum photoresponse, critical for the efficient utilization of solar energy in hydrogen production.This study focused on optimizing the photoanode materials by improving the intrinsic properties of LHPs through bandgap tuning and enhanced charge transfer to the oxygen evolution reaction (OER) catalyst. However, the operational stability of LHPs in PEC applications poses a formidable challenge, primarily due to vulnerability to moisture-induced degradation.Addressing the stability concerns, some researches about application of ultrathin Ni surface layers and the use of low-melting-point field metals for protective encapsulation are reported. However, these methods have shown limited success in preventing moisture-induced degradation. In response, this work proposes the innovative use of conductive carbon poweder (CCP) as a superior alternative for enhancing electrical connectivity and stability between LHP solar cells and the OER catalyst.Our findings reveal that CCP's superior conductivity facilitates efficient charge transfer from LHP-based solar cells to OER catalysts, maintaining negligible current and voltage loss. To optimize the LHP photoanode's performance, we focused on enhancing the individual efficiencies and stabilities of the PSC and OER catalyst components. For the PSC, we improved stability by integrating a smaller cation (methylammonium, MA) into the FAPbI3 (formamidinium, FA) lattice, thereby stabilizing the α-phase and enhancing hydrogen bonding. This modification was substantiated through various spectroscopic and X-ray diffraction. Meanwhile, the OER catalyst's efficiency was amplified by employing a 3D-structured NiFe on an Ni foil substrate, improving catalytic activity and stability through enhanced hole mobility and increased electrochemically active surface area.The integrated LHP photoanode demonstrated a notable onset potential of 0.56 V and a peak photocurrent density of 24.26 mA/cm² at 1.23 V vs RHE, achieving a 9.16% applied bias photon-to-current efficiency and sustained performance over 48 hours in a pH 14 aqueous solution under simulated solar illumination. This performance is attributed to the synergistic effect of the optimized PSC and OER catalyst, facilitated by CCP's efficient electrical connectivity.

A Versatile Photoelectrochemical System with Feooh/MoOx/BiVO4 for Reactive Halogen Species Generation Coupled with Hydrogen Evolution

Solar-driven seawater splitting is a promising approach for sustainable green hydrogen generation. Chlorine evolution reaction (ClER) can provide much faster kinetics than oxygen evolution reaction (OER), due to lower number of electrons involved in the interfacial charge transfer. Designing stable and efficient photoelectrodes for a photoelectrochemical (PEC) seawater splitting presents challenges due to the corrosive nature of seawater. BiVO4 has been a promising photoanode for solar energy conversion to molecular hydrogen (H2), due to desirable bandgap (2.4 eV), favorable band position and chemical stability. Nevertheless, BiVO4 has been mostly employed for OER, and shows limitation of poor charge transport and insufficient active sites for interfacial charge transfer. This study proposed a composite photoanode comprising MoOx hole transfer layer and iron oxyhydroxide (FeOOH) electrocatalysts on BiVO4, to enhance photocurrent and stability in the PEC seawater splitting. The MoOx layer, containing Mo6+ as electron donors, was deposited on BiVO4 using a simple drop-casting method. A simple reductive electrodeposition introduced the FeOOH electrocatalysts, while simultaneously forming MoOx with surface defect states (FeOOH/MoOx/BiVO4) to facilitate the facilitating hole transfer through the segregated MoOx layer. The surface structure of FeOOH/MoOx/BiVO4 photoanode was investigated through scanning electron microscopy (SEM) and transmission electron microscopy (TEM). X-ray photoelectron spectroscopy (XPS) confirmed successful synthesis of MoOx and FeOOH layers on BiVO4. The charge separation efficiency was four times higher on the FeOOH/MoOx/BiVO4 photoanode (78%) compared to the intact BiVO4 photoanode (18%). Additionally, the FeOOH/MoOx/BiVO4 photoanode exhibited improved photocurrent density for OER and ClER under simulated AM 1.5 G sunlight, reaching 3.3 mA cm-2 at 1.23 VRHE in circum-neutral pH, which is approximately three times higher than that of the intact BiVO4. The applied bias photon-to-current efficiency (ABPE) of the FeOOH/MoOx/BiVO4 photoanode reached 0.9% at 1.23 VRHE, five times higher than that of intact BiVO4. Such excellent PEC activity can be ascribed to introduced surface defects (such as oxygen vacancy) on MoOx/BiVO4 and alleviated kinetic barrier by FeOOH. Moreover, the photocurrent density of the FeOOH/MoOx/BiVO4 photoanode in a 0.5 M NaCl electrolyte (for ClER) was 0.5 mA cm-2 higher than that in 0.5 M Na2SO4 electrolyte (for OER). Transient absorption spectroscopy (TAS) confirmed the improved charge transport behavior of the modified BiVO4 for OER or ClER. The generation of reactive chlorine species could compromise the stability of FeOOH, which could be mitigated by an added aqueous pollutants. For instance, in the PEC chlorine evolution reaction system, ammonia or 4-chlorophenol as model pollutant enhanced the stability. Notably, the FeOOH/MoOx/BiVO4 exhibited a 10-fold higher rate for ammonia oxidation compared to the intact BiVO4. A moderated concentration of bromide ion could further elevate the photocurrent density. The increased photocurrent activity of the modified FeOOH/MoOx/BiVO4 photoanode in PEC splitting of blended seawater and wastewater can serve multifaceted purposes, enhancing the efficiency of pollutants degradation (or chemical upgrading) and H2 evolution.

3D-Printed High Surface Area Electrodes and Advanced Flow Reactors for Bio-Compatible Electrochemical Reactions

With the urgent need for emissions-free economies, bio-catalytic electrochemical processes such as electro-bio-methanation enable coupling of renewable energy harvesting with chemical energy storage and/or chemical synthesis. Electro-bioreactors offer high product selectivity and efficiency, eliminating the need for energy intensive separations. However, the electrochemical reaction rates of bio-catalytic processes are fundamentally constrained due to poor fluid distribution and ion transport near the electrode surface. Mass transport limitations in bioreactors alter the reactive surface environments and cause bio-catalytic stability issues. To address these challenges and achieve high volumetric productivities under bio-compatible conditions, we introduced additively manufactured, high surface area 3D electrodes and engineered flow cells. We characterized the effects of electrode geometry and structural parameters on electrochemical performance in abiotic media to develop structure property relationships. Using the hydrogen evolution reaction as a model system, we identified several high surface area structures that improve the fluid distribution within the reactor. Triply periodic minimal surface structures, like gyroids, enable higher volumetric productivities compared to conventional planar electrodes. These findings can be used to understand the role of electrode structure on electrochemical performance and the scaling behavior or bio-reactor flow cells utilizing 3D electrodes.This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344

Fabrication of PbS QD-Mediated Organic-Inorganic Hybrid Swir Opds Using Azide Functional Ligand (FPA-S) and Study of Polymer Morphology Control

The efficiency of exciton dissociation and electron mobility in organic photodetectors (OPDs) is critically dependent on the microscale morphology of the interpenetrating network structures between electron donor and acceptor materials. Therefore, understanding the impact of phase separation within the active layer and the interactions between components is crucial for OPD performance.In this study, we propose a hybrid Short Wavelength Infrared (SWIR) photodiode that utilizes PbS quantum dots (QDs) minimally, leveraging their exceptional SWIR absorption properties, alongside an organic semiconductor matrix to counterbalance their poor charge transport characteristics. While similar concepts of organic-inorganic hybrid photodiodes have been suggested previously, the straightforward blending of organic semiconductors and QDs has been constrained by poor miscibility due to differences in surface energy between organic and inorganic phases. This results in reduced phase stability post-film fabrication and significant phase separation. Therefore, we introduce an azide-functional ligand (FPA-S) capable of coordinating with QDs and bonding with polymers via azide groups, to induce photo-crosslinking and suppress phase separation between polymers and QDs.Effectively separating excitons while minimizing the amount of PbS QDs, which are toxic and exhibit low charge mobility, necessitates controlling the morphology of the active layer. We optimized conditions such as solvent type, evaporation rate, volume ratio, and external humidity based on a quaternary phase diagram derived from Flory-Huggins interaction parameters. Additionally, we sought to identify the optimal condition by calculating the equilibrium state of the phase-separated structure of polymers using a phase-field model with the Ising machine.

Enhancing Photoelectrocatalytic Efficiency of BiVO4 Photoanodes by Crystal Orientation Control.

Bismuth Vanadate (BiVO4) is a promising photoanode material due to its stability and suitable bandgap, making it effective for visible light absorption. However, its photoelectrocatalytic efficiency is often limited by the poor transport dynamics of photogenerated carriers. Recent research found that varying the atomic arrangement in crystals and Fermi levels across different crystal orientations can lead to significant differences in carrier mobility, charge recombination rates, and overall performance. In this work, we optimized the atomic arrangement by controlling the crystal growth direction to improve carrier separation efficiency using a wet chemical method. Systematic investigations revealed that the preferential [010]-oriented BiVO4 film exhibits the highest carrier mobility and photocurrent density. Under an applied bias of 1.21 V (vs. RHE) in a 0.5 M Na2SO4 electrolyte, it achieved a photocurrent density of 0.2 mA cm-2 under AM 1.5 G illumination, significantly higher than that of the [121]-oriented (0.056 mA cm-2) and randomly oriented films (0.11 mA cm-2). This study provides a deeper understanding of the role of crystal orientation in enhancing photoelectrocatalytic efficiency.

Commonalities and Characteristics Analysis of Fluorine and Iodine used in Lithium‐Based Batteries

AbstractAmong optimization strategies for solving the poor ion transport ability and electrolyte/electrode interface compatibility problems of lithium (Li)‐based batteries, halogen elements, such as fluorine (F) and iodine (I), have gradually occupied an important position because of their superb electronegativity, oxidizability, ionic radius, and other properties. The study commences by outlining the shared mechanism by which F and I enhance solid‐state lithium metal batteries' electrochemical performance. In particular, F and I can considerably improve ion transport capacity through chemical means such as intermolecular interactions and halogenation reactions. Furthermore, the utilization of F and I significantly enhances the stability of the electrolyte/electrode interface via physical strategies, encompassing doping techniques, the application of surface coatings, and the fabrication of synthetic intermediate layers. Subsequently, the characteristics of F and I used in Li‐based batteries are elaborated in detail, focusing on the fact that F can provide additional energy density as an anode material but by different mechanisms. Additionally, I can considerably activate dead lithium at the negative electrode, and F can act as a new carrier. Finally, a rational concept of the synergistic effect of F and I is proposed and the feasibility of F–I bihalide solid electrolytes is explored.