Age-related effects of Mycoplasma pneumoniae infection and subsequent asthma exacerbation in children.

BACKGROUND: Mycoplasma pneumoniae causes community-acquired pneumonia in children and increases asthma risk, but large studies are lacking. OBJECTIVE: To assess the link between M. pneumoniae infection and to asthma exacerbation, in children with allergies, and age of infection impact. METHODS: This retrospective cohort study analyzed medical records of South Korean children between January 2002 and December 2017. The study's exposure was hospitalization with an M. pneumoniae-related diagnosis, and the outcome was defined as asthma exacerbation, confirmed by hospitalization at least 6 months after M. pneumoniae infection, with alternative validation using asthma diagnosis and systemic steroid prescription records. Hazard ratios (HRs) for asthma exacerbation risk were estimated for the matched cohort using a Cox proportional hazards model stratified by allergic comorbidities. Time-dependent covariates and age-stratified exposure groups were used to calculate odds ratios. RESULTS: The study included 84,074 children with M. pneumoniae infection and 336,296 unexposed children. Follow-up for 12.2 ± 2.3 years found the exposed group had a significant risk of asthma exacerbation (HR 2.86, 95% confidence interval [CI] 2.67-3.06) regardless of allergic comorbidities. The risk was highest (over threefold) in children infected between 24 and 71 months. Sensitivity analysis using an alternative definition of the outcome showed an HR of 1.38 (95% CI 1.35-1.42), further supporting the association between M. pneumoniae infection and asthma exacerbation. CONCLUSION: M. pneumoniae infection was significantly associated with an increased risk of subsequent asthma exacerbation regardless of allergic comorbidities. Further research needed for understanding and confirmation.

The KAAACI Guidelines for Sublingual Immunotherapy.

Allergen immunotherapy is regarded as the only disease-modifying treatment option for various allergic conditions, including allergic rhinitis and asthma. Among the routes of administration of allergens, sublingual immunotherapy (SLIT) has gained clinical interest recently, and the prescription of SLIT is increasing among patients with allergies. After 30 years of SLIT use, numerous pieces of evidence supporting its efficacy, safety, and mechanism allows SLIT to be considered as an alternative option to subcutaneous immunotherapy. Based on the progressive development of SLIT, the current guideline from the Korean Academy of Asthma, Allergy, and Clinical Immunology aims to provide an expert opinion by allergy, pediatrics, and otorhinolaryngology specialists with an extensive literature review. This guideline addresses the use of SLIT, including 1) mechanisms of action, 2) appropriate patient selection for SLIT, 3) the currently available SLIT products in Korea, and 4) updated information on its efficacy and safety. This guideline will facilitate a better understanding of practical considerations for SLIT.

First-principles study on the design of nickel based bimetallic catalysts for xylose to xylitol conversion.

A significant challenge for effective biomass utilization and upgrading is catalysis. This research paper focuses on the conversion of xylose into xylitol, a valuable chemical used in the pharmaceutical and food industries. The primary objective is to design more efficient and cost-effective catalysts for this conversion process. The study investigates the use of Ni-bimetallic catalysts by employing a first-principles technique. Catalyst models derived from subsets of Ni (111) surfaces with various transition metals (M = Ti, V, Cr, Fe, Co, and Cu) are examined. The catalyst surfaces are screened based on the rate-determining step (RDS) involved in the conversion of xylose to xylitol, with Ni (111) serving as a reference. Electronic structure calculations are used to analyze the activities of the investigated Ni-bimetallic catalysts relative to the RDS. The results show that certain bimetallic surfaces exhibit significantly lower kinetic barriers compared to the Ni (111) surface. The hydrogenation process when investigated using different transition state paths, reveals that hydrogenation commences at the carbon atom of the carbonyl group of xylose after the ring-opening step. Stability segregation tests demonstrate varying behaviors among the screened catalysts, with Ni (111)/Cr/Ni showing greater stability than Ni (111)/Co. This study sheds light on the theoretical design of catalysts for xylose conversion, providing insights for the development of more efficient and active catalysts for industrial applications. The research highlights the significance of theoretical methodologies in tailoring catalyst surfaces to optimize their performance in biomass upgrading.

Investigating the occurrence of autoimmune diseases among children and adolescents hospitalized for Mycoplasma pneumoniae infections.

Background: Mycoplasma pneumoniae infection is common in the general population and may be followed by immune dysfunction, but links with subsequent autoimmune disease remain inconclusive. Objective: To estimate the association of M. pneumoniae infection with the risk of subsequent autoimmune disease. Methods: This retrospective cohort study examined the medical records of South Korean children from 01/01/2002 to 31/12/2017. The exposed cohort was identified as patients hospitalized for M. pneumoniae infection. Each exposed patient was matched with unexposed controls based on birth year and sex at a 1:10 ratio using incidence density sampling calculations. The outcome was subsequent diagnosis of autoimmune disease, and hazard ratios (HRs) were estimated with control for confounders. Further estimation was performed using hospital-based databases which were converted to a common data model (CDM) to allow comparisons of the different databases. Results: The exposed cohort consisted of 49,937 children and the matched unexposed of 499,370 children. The median age at diagnosis of M. pneumoniae infection was 4 years (interquartile range, 2.5-6.5 years). During a mean follow-up time of 9.0 ± 3.8 years, the incidence rate of autoimmune diseases was 66.5 per 10,000 person-years (95% CI: 64.3-68.8) in the exposed cohort and 52.3 per 10,000 person-years (95% CI: 51.7-52.9) in the unexposed cohort, corresponding to an absolute rate of difference of 14.3 per 10,000 person-years (95% CI: 11.9-16.6). Children in the exposed cohort had an increased risk of autoimmune disease (HR: 1.26; 95% CI: 1.21-1.31), and this association was similar in the separate analysis of hospital databases (HR: 1.25; 95% CI 1.06-1.49). Conclusion: M. pneumoniae infection requiring hospitalization may be associated with an increase in subsequent diagnoses of autoimmune diseases.

KAAACI Guidelines for Allergen Immunotherapy.

Allergen immunotherapy (AIT) is a causative treatment for various allergic diseases such as allergic rhinitis, allergic asthma, and bee venom allergy that induces tolerance to offending allergens. The need for uniform practice guidelines in AIT is continuously growing because of the increasing discovery of potential candidates for AIT and evolving interest in new therapeutic approaches. This guideline is an updated version of the Korean Academy of Asthma Allergy and Clinical Immunology recommendations for AIT published in 2010. This updated guideline proposes an expert opinion by allergy, pediatrics, and otorhinolaryngology specialists with an extensive literature review. The guideline deals with basic knowledge and methodological aspects of AIT, including mechanisms, clinical efficacy, patient selection, allergens extract selection, schedule and doses, management of adverse reactions, efficacy measurements, and special consideration in pediatrics. The guidelines for sublingual immunotherapy will be covered in detail in a separate article.

Current Status of the Pediatric Palliative Care Pilot Project in South Korea Based on the Experience of a Single Center.

Purpose: We evaluated the status of patients enrolled in South Korea's pediatric palliative care pilot project based on the experience of a single center. This study examined factors related to end-of-life services and differences in medical costs. Methods: The medical records of 120 patients referred by a pediatric palliative care team were analyzed retrospectively. Data from July 1 to February 28, 2022 were collected and analyzed using the chi-square test and the Mann-Whitney U test. Results: Volunteer programs and psychological support (100%), family support and education (99.2%), and financial support through institutional linkage (62.5%) were provided to the participants. In the deceased group, there were no significant differences in general characteristics, which included age, gender, primary disease, religion, duration of hospitalization in an intensive care unit (ICU) and non-intensive care unit (non-ICU). However, the ICU group had fewer opportunities to access individual pain and physical symptom management than the non-ICU group and there were limitations in linking with external resources. Medical expenses were significantly different for the ICU group, with a 3-times higher average cost than the non-ICU group. Conclusion: Although an individualized approach is needed for each patient in pediatric palliative care, psychosocial care is essential. In addition, if early intervention for end-of-life pediatric patients is available from a palliative care team, the cost burden of medical care for patients and their families should be minimal.

In situ fabrication of Ag decorated porous ZnO photocatalyst via inorganic-organic hybrid transformation for degradation of organic pollutant and bacterial inactivation.

In this study, in situ silver (Ag) - porous ZnO photocatalysts were synthesized via solvothermal and post-annealing treatment. The formation of the porous ZnO structure due to the removal of organic moieties from the inorganic-organic hybrids Ag-ZnS(en)0.5 during the annealing process. The optimal Ag-ZnO photocatalyst showed excellent photocatalytic degradation activity, with 95.5% orange II dye and 97.2% bisphenol A (BPA) degradation under visible light conditions. Additionally, the photocatalytic inactivation of Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) led to a 97% inactivation rate after 2 h under dark conditions. Trapping experiments suggest that the superoxide anion (O2-) radicals are the main active species to degrade the organic dye. The improved photocatalytic dye degradation activity and inactivation of bacteria were attributed to the synergistic effect of Ag and porous ZnO structure, increased surface area, and efficiently separated the photoexcited charge carriers. This work could provide an effective strategy for the synthesis of porous structures toward organic pollutant degradation and bacterial inactivation in wastewater.

[Analysis of ROX Index, ROX-HR Index, and SpO2/FIO2 Ratio in Patients Who Received High-Flow Nasal Cannula Oxygen Therapy in Pediatric Intensive Care Unit].

PURPOSE: This study aimed to evaluate the use of the respiratory rate oxygenation (ROX) index, ROX-heart rate (ROX-HR) index, and saturation of percutaneous oxygen/fraction of inspired oxygen ratio (SF ratio) to predict weaning from high-flow nasal cannula (HFNC) in patients with respiratory distress in a pediatric intensive care unit. METHODS: A total of 107 children admitted to the pediatric intensive care unit were enrolled in the study between January 1, 2017, and December 31, 2021. Data on clinical and personal information, ROX index, ROX-HR index, and SF ratio were collected from nursing records. The data were analyzed using an independent t-test, χ² test, Mann-Whitney U test, and area under the curve (AUC). RESULTS: Seventy-five (70.1%) patients were successfully weaned from HFNC, while 32 (29.9%) failed. Considering specificity and sensitivity, the optimal cut off points for predicting treatment success and failure of HFNC oxygen therapy were 6.88 and 10.16 (ROX index), 5.23 and 8.61 (ROX-HR index), and 198.75 and 353.15 (SF ratio), respectively. The measurement of time showed that the most significant AUC was 1 hour before HFNC interruption. CONCLUSION: The ROX index, ROX-HR index, and SF ratio appear to be promising tools for the early prediction of treatment success or failure in patients initiated on HFNC for acute hypoxemic respiratory failure. Nurses caring for critically ill pediatric patients should closely observe and periodically check their breathing patterns. It is important to continuously monitor three indexes to ensure that ventilation assistance therapy is started at the right time.

Porous Zn1-xCdxSe/ZnO Nanorod Photoanode Fabricated from ZnO Building Blocks Grown on Zn Foil for Photoelectrochemical Solar Hydrogen Production.

Solar energy is the most promising, efficient, environmentally friendly energy source with the potential to meet global demand due to its non-polluting nature. Herein, a porous Zn1-xCdxSe/ZnO nanorod (NR) heterojunction was synthesized by hydrothermal and low-temperature solvothermal methods. First, the ZnO NR was grown on a Zinc foil, and an inorganic-organic hybrid ZnSe(en)0.5 material was developed by the low-temperature solvothermal method. In this work, the ZnO NR acted as a base material and a building block for the growth of ZnSe(en)0.5. Moreover, after the solvothermal process, the reduced Se2- reacts with the ZnO NR and forms inorganic-organic hybrid ZnSe(en)0.5. After the selenization process, the obtained material shows a red brick color due to the absorbance of excessive Se metal particles during the solvothermal process. Furthermore, in order to enhance the photoelectrochemical properties, the Cd2+ ion exchange method was applied at various temperatures (140, 160, and 180 °C for 3 h) to produce a precursor material to a porous Zn1-xCdxSe/ZnO NR nanostructure. The optimum Zn1-xCdxSe/ZnO NR-160 photoanode showed a high photocurrent density of 7.8 mA·cm-2 at -0.5 V vs. Ag/AgCl with a hydrogen evolution rate of 199 µmol·cm-2/3 h. The improved photocurrent performance was attributed to effective light absorption and prolonged recombination lifetime.

Infant Feeding Pattern Clusters Are Associated with Childhood Health Outcomes.

(1) Background: Feeding behavior habits have a pattern with a certain tendency during infancy. We aimed to identify the associations between feeding patterns in infancy and the subsequent 10-year childhood disease burden. (2) Methods: Data from 236,372 infants were obtained from the national health insurance and screening program records in South Korea. Parent-administered questionnaires during infancy provided details on the feeding type and types/frequency of complementary food for analyzing feeding patterns. The outcomes were all-cause hospitalization and the development of 15 representative childhood diseases until the age of 10 years. Anthropometric measurements obtained at 6 years of age were analyzed. To estimate outcome risks while considering multiple risk factors, we employed a Cox proportional hazard and modified Poisson regression. (3) Results: Three clusters were identified: high prevalence of breastfeeding with regular exposure to a variety of solid foods (n = 116,372, cluster 1), similar prevalence of breastfeeding and formula feeding with less exposure to solid foods (n = 108,189, cluster 2), and similar prevalence of breastfeeding and formula feeding with the least exposure to solid foods in infancy (n = 11,811, cluster 3). Compared with cluster 1, children in clusters 2 and 3 had increased risks of all-cause hospitalization (hazard ratio (HR), (95% confidence interval (CI)), 1.04 (1.03-1.06) and 1.08 (1.05-1.11), respectively). Children in clusters 2 and 3 had an increased risk of upper respiratory infection, pneumonia, and gastroenteritis, as well as neurobehavioral diseases. Overweight/obesity at the age of 6 years was associated with clusters 2 and 3. (4) Conclusions: Feeding patterns in infancy were associated with an increased risk of childhood disease burden.

Epidemiology of patients with asthma in Korea: Analysis of the NHISS database 2006-2015.

Background: There has been a concerning increase in the prevalence and socioeconomic burden of asthma in Korea. Korea's National Health Insurance System (NHIS) covers insurance payment and claims management for all Koreans. Using National Health Insurance Sharing Service (NHISS) claims data. This study aimed to investigate patterns of healthcare utilization and direct cost in patients with asthma over a 10-year period. Methods: In this retrospective population-based study, we examined NHISS claims records between July 2005 and June 2016 and investigated healthcare utilization among patients with asthma based on age group and severity of disease (non-severe asthma [NSA] and severe asthma [SA]). Results: From 2006 to 2015, the total number of patients with asthma in Korea steadily increased from 743 968 to 2 286 309, with a corresponding increase in prevalence from 1.62% to 4.74%. The proportion of patients with SA decreased from 3.16% in 2006 to 1.56% in 2015; the proportion was consistently higher in men than in women. In addition, patients with SA had a higher cost per outpatient visit than patients with NSA, and the number of outpatient visits per year increased. The inhaled corticosteroid (ICS) prescription rate among patients with asthma decreased from 22.9% in 2006 to 15.7% in 2015. Furthermore, for a period of 10 years, more than 40% of patients with SA have been prescribed short-acting ß-2 agonists (SABAs). Conclusions: Although patients with SA comprised a small proportion of patients with asthma, they incurred greater medical costs per person. The pharmaceutical prescription pattern indicated a lack of ICS-based prescriptions and frequent SABA prescriptions.

Synergistic role of hydrogen treatment and heterojunction in H-WO3-x/TiO2-x NT/Ti foil-based photoanodes for photoelectrochemical wastewater detoxification and antibacterial activity.

The process of photoelectrochemical wastewater detoxification is limited by significant charge recombination, which is difficult to suppress with efficient single-material photoanodes. We demonstrated the effectiveness of hydrogen treatment in evaluating charge separation properties in WO3-x/TiO2-x NT/Ti foil heterojunction photoanodes. The influence of varying hydrogen annealing (200-400 °C) on the structural and photoelectrochemical properties of WO3/TiO2 NS/NT heterojunction is studied systematically. Additionally, after hydrogen treatment of pristine WO3/TiO2 NT/Ti foil photoanodes, substoichiometric H-WO3-x/TiO2-x NT-300 achieved the 1.21 mA/cm2 photocurrent density, which is 8.06 and 3.27 times than TiO2 NT and WO3/TiO2 NT. The hydrogen-treated H-WO3-x/TiO2-x NT-300 electrode exhibits 3 times greater bulk efficiencies than the WO3/TiO2 NT electrode due to the production of oxygen vacancies at the interface. Additionally, optimum H-WO3-x/TiO2-x NS/NT-300 photoanode exhibited 93.8% E. coli and 99.8% BPA decomposition efficiencies. The present work shows the effectiveness of microwave-assisted H-WO3-x/TiO2-x NT heterojunction photoanodes for organic decomposition and antibacterial activity in a neutral environment without surface-loaded co-catalysts.

Synergistic role of in-situ Zr-doping and cobalt oxide cocatalysts on photocatalytic bacterial inactivation and organic pollutants removal over template-free Fe2O3 nanorods.

Herein, we synthesized in-situ Zr-doped Fe2O3 NRs photocatalyst by successive simple hydrothermal and air quenching methods. The synergistic roles of CoOx (1 wt%) and Zr-doping on bacteria inactivation and model organic pollutants over Fe2O3 NRs photocatalyst were studied in detail. Initially, rod-like Zr ((0-8) %)-doped Fe2O3 NRs were produced via a hydrothermal method. CoOx was loaded onto the Zr ((0-8) %)-doped Fe2O3 NRs) surface by a wet impregnation approach. The Zr-doping conditions and CoOx loadings were judiciously optimized, and a highly photoactive CoOx(1 wt%)/Zr(6%)-doped Fe2O3 NRs photocatalyst was developed. The CoOx(1 wt%) loaded Zr(6%)-doped Fe2O3 NRs photocatalyst revealed 99.4% inactivation efficiency compared with (0, 4 and 8)% Zr-doped Fe2O3 NRs, respectively. After CoOx(1 wt%)/Zr(6%)-doped Fe2O3 NRs photocatalyst treatment, Bio-TEM images of bacterial cells showed extensive morphological deviations in cell membranes, compared with the non-treated ones. Additionally, the optimum CoOx(1 wt%)/Zr(6%)-doped Fe2O3 NRs photocatalyst exhibited 99.2% BPA and 98.3% orange II dye degradation after light radiation for 3 h. This work will provide a rapid method for the development of photostable catalyst materials for bacterial disinfection and organic degradation.

Maternal Posttraumatic Stress Symptoms and Psychological Burden in Mothers of Korean Children With Anaphylaxis.

PURPOSE: Anaphylaxis is a severe allergic reaction that is potentially life-threatening, but post-traumatic stress symptoms (PTSS) in the caregivers of children with anaphylaxis have not been evaluated. This study aimed to investigate the psychological burden on mothers of children with recent anaphylaxis. METHODS: A total of 188 children with recent anaphylaxis was recruited from 13 hospitals in Korea. Validated questionnaires, including the Korean versions of the Beck Anxiety Inventory (K-BAI), the Beck Depression Inventory (K-BDI), and the Impact of Event Scale Revised-Korean version (IES-R-K), were used to evaluate maternal anxiety, depression, and PTSS. RESULTS: The median ages of children and their mothers were 4 and 36 years, respectively. PTSS (IES-R-K ≥ 25) were identified in 56.9% of mothers, and 57.9% of them showed severe PTSS. The proportions of mothers who had anxiety (K-BAI ≥ 22) and depression (K-BDI ≥ 17) were 18.6% and 33.0%, respectively. Multivariable logistic regression analysis indicated that the patient's history of asthma (adjusted odds ratio [aOR], 5.46; 95% CI, 1.17-25.59) and the presence of central nervous symptoms (aOR, 3.27; 95% CI, 1.07-9.96) were associated with PTSS. Age of 2 or older (aOR, 2.87; 95% CI, 1.10-7.52) and eggs, milk, or wheat as the cause of anaphylaxis (aOR, 2.87; 95% CI, 1.10-7.52) increased the risk of severe PTSS. CONCLUSIONS: The rate of PTSS among mothers of children with recent anaphylaxis was high at 56.9%. Clinicians who care for pediatric anaphylaxis patients should be aware of the psychological burden on their caregivers.

First-principles design of hetero CoM (M = 3d, 4d, 5d block metals) double-atom catalysts for oxygen evolution reaction under alkaline conditions.

As an extension of single-atom catalysts, the development of double-atom catalysts with high electrocatalytic activity for the oxygen evolution reaction (OER) is vital to facilitate hydrogen production and industrial applications. The CoM (M = 3d, 4d, 5d block metals) homo and double-atom catalysts supported on nitrogen-doped graphene (CoM/N4G) were prepared for electrochemical water oxidation under alkaline conditions, and the electrocatalytic activity was studied through density functional theory (DFT) calculations. The hetero CoCu/N4G double-atom catalyst indicated the highest OER activity with an onset potential of 0.83 V, while the homo Co2/N4G catalyst showed a higher onset potential of 1.69 V. The decoupled strain, dopant, and configurational effects based on the notable differences between the homo Co2/N4G and CoCu/N4G explained the enhanced OER activity, implying that the Cu dopant has a crucial impact on boosting the reactivity by reducing the affinity of reaction intermediates. The enhancement could also be understood from the perspective of the electron structure characteristic through d-orbital resolved density of states (ORDOS) (d z 2 , d xz , d yz , d xy , and d x 2-y 2 ) analysis. From the ORDOS analysis, we found an apparent alteration of the key orbitals between Co2/N4G (d z 2 , d xz , and d yz ) and CoCu/N4G (d z2, d xz , d yz , and d xy ) with a substantial change in the overlap ratio (X d). This theoretical study offers beneficial insights into developing a strategy for efficient OER catalysts utilizing a double-atom structure.

Experimental and Numerical Study of Pd/Ta and PdCu/Ta Composites for Thermocatalytic Hydrogen Permeation.

The development of stable and durable hydrogen (H2) separation technology is essential for the effective use of H2 energy. Thus, the use of H2 permeable membranes, made of palladium (Pd), has been extensively studied in the literature. However, Pd has considerable constraints in large-scale applications due to disadvantages such as very high cost and H2 embrittlement. To address these shortcomings, copper (Cu) and Pd were deposited on Ta to fabricate a composite H2 permeable membrane. To this end, first, Pd was deposited on a tantalum (Ta) support disk, yielding 7.4 × 10-8 molH2 m-1 s-1 Pa-0.5 of permeability. Second, a Cu-Pd alloy on a Ta support was synthesized via stepwise electroless plating and plasma sputtering to improve the durability of the membrane. The use of Cu is cost-effective compared with Pd, and the appropriate composition of the PdCu alloy is advantageous for long-term H2 permeation. Despite the lower H2 permeation of the PdCu/Ta membrane (than the Pd/Ta membrane), about two-fold temporal stability is achieved using the PdCu/Ta composite. The degradation process of the Ta support-based H2 permeable membrane is examined by SEM. Moreover, thermocatalytic H2 dissociation mechanisms on Pd and PdCu were investigated and are discussed numerically via a density functional theory study.

Single-Step Fabrication of Polymeric Composite Membrane via Centrifugal Colloidal Casting for Fuel Cell Applications.

Recent interest in polymer electrolyte membranes (PEMs) for fuel cell systems has spurred the development of infiltration technology by which to insert ionomers into mechanically robust reinforcement structures by solution casting in order to produce a cost effective and highly efficient electrolyte. However, the results of the fabrication process often continue to present challenges related to the structural complexity and self-assembly dynamics between the hydrophobic and hydrophilic parts of the constituents which in turn, necessitates additional processing steps and increases production costs. Here, a single-step process is reported for highly compact polymeric composite membranes (PCMs), fabricated using a centrifugal colloidal casting (C3) method. Combined structural analyses as well as coarse-grained molecular dynamics simulations are employed to determine the micro-/macroscopic structural characteristics of the fabricated PCMs. These findings indicate that the C3 method is capable of forming highly dense ionomer matrix-reinforcement composites consisting of microphase-separated ionomer structures with tailored crystallinity and ionic cluster sizes. An outcome that is very unlikely with the single-step coating steps in conventional methods. These structural attributes ensure PCMs with better proton conductivity, greater strain stability, and lower gas crossover properties compared to commercial pristine membranes, expanding their possible range of applicability to PEMs.

Conversion of cyclic xylose into xylitol on Ru, Pt, Pd, Ni, and Rh catalysts: a density functional theory study.

There is currently no theoretical study on the hydrogenation of xylose to xylitol on a catalyst's surface, limiting proper understanding of the reaction mechanisms and the design of effective catalysts. In this study, DFT techniques were used for the first time to investigate the mechanisms of xylose to xylitol conversion on five notable transition metal (TM) surfaces: Ru(0001), Pt(111), Pd(111), Rh(111), and Ni(111). Two transition state (TS) paths were investigated: TS Path A and TS Path B. The TS Path B, which was further subdivided into TS Path B1 and B2, was proposed to be the minimum energy path (MEP) for the reaction process. According to our computational results, the MEP for this reaction begins with the structural rearrangement of cyclic xylose into its acyclic form prior to step-wise hydrogenation. The rate-determining step (RDS) on Ru(0001), Pt(111), Pd(111), and Ni(111) was discovered to be the ring-opening process via C-O bond scission of cyclic xylose. On Rh(111), however, the RDS was found to be the first hydrogenation stage, leading to the hydrogenation intermediate. Furthermore, based on the RDS barrier, our results revealed that the activities of the tested TM surfaces follow the trend: Ru(0001) > Rh(111) ≥ Ni(111) > Pd(111) > Pt(111). This result demonstrates the higher activity of Ru(0001) compared to other surfaces used for xylose hydrogenation. It correlates with experimental trends in relation to Ru(0001) superiority and provides the basis for understanding the theoretical design of economical and more active catalysts for xylitol production.

Topotactic and Self-Templated Fabrication of Zn1-xCdxSe Porous Nanobelt-ZnO Nanorod for Photoelectrochemical Hydrogen Production.

Herein, we propose the topotactic and self-templated fabrication of Zn1-xCdxSe porous nanobelt-ZnO nanorod (termed as ZnCdSe/ZnO) photoelectrode via the cadmium (Cd2+) ion-exchange process on zinc (Zn) foil. Inorganic-organic hybrid ZnSe(en)0.5 nanobelt (NB) was synthesized on Zn foil by a facial solvothermal method at different temperatures of 140, 160, and 180 °C for 12 h. The interfacial properties and photoelectrochemical (PEC) performance of inorganic-organic ZnSe(en)0.5 NB fabricated through the Cd2+ ion-exchange method at different time durations of 6, 12, 18, and 24 h at 140 °C were investigated. The TEM analysis results indicate that the inorganic-organic ZnSe(en)0.5 NB transformed into ZnCdSe and a self-assembled ZnO formed on the Zn foil. In particular Cd2+ ion temperature (140 °C/18 h), the optimized ZnCdSe/ZnO-(F) photoelectrode shows an excellent photocurrent density of 14 mA·cm-2 at 0 V vs Ag/AgCl with 219 µmol·cm-2 hydrogen gas evolution for 3 h under 1 sun illumination. The higher photocurrent value resulted from the optimum growth of ZnO, the formation of porous ZnCdSe, and the effective electrolyte penetration for electron-hole pair separation. The photoluminescence spectroscopy shows that the photoexcited charged carriers promoted a longer lifetime. Furthermore, we provide a full account of the possible charge-transfer mechanism during PEC hydrogen production.

Lowering the onset potential of Zr-doped hematite nanocoral photoanodes by Al co-doping and surface modification with electrodeposited Co-Pi.

Herein, in situ zirconium-doped hematite nanocoral (Zr-Fe2O3 (I) NC) photoanode was prepared via a specially designed diluted hydrothermal approach and modified with Al3+ co-doping and electrodeposited cobalt-phosphate ("Co-Pi") cocatalyst. Firstly, an unintentional in situ Zr-Fe2O3 (I)) NC photoanode was synthesized, which achieved an optimum photocurrent density of 0.27 mA/cm2 at 1.0 V vs. RHE but possessed a more positively shifted onset potential than conventionally prepared hematite nanorod photoelectrodes. An optimized amount of aluminum co-doping suppresses the bulk as well as surface defects, which causes a negative shift in the onset potential from 0.85 V to 0.8 V vs. RHE and enhances the photocurrent density of Zr-Fe2O3(I) NC from 0.27 mA/cm2 to 0.7 mA/cm2 at 1.0 V vs. RHE. The electrodeposited Co-Pi modification further reduce the onset potential of Al co-doped Zr-Fe2O3(I) NC to 0.58 V vs. RHE and yield a maximum photocurrent of 1.1 mA/cm2 at 1.0 V vs. RHE (1.8 mA/cm2 at 1.23 V vs RHE). The improved photocurrent at low onset potential can be attributed to synergistic effect of Al co-doping and Co-Pi surface modification. Further, during photoelectrochemical water-splitting, a 137 and 67 µmol of hydrogen (H2) and oxygen (O2) evolution was achieved over the optimum Co-Pi-modified Al-co-doped Zr-Fe2O3(I) NC photoanode within 6 h. The proposed charge transfer mechanism in optimum Co-Pi-modified Alco-doped Zr-Fe2O3(I) NC photoanodes during the photoelectrochemical water splitting was also studied.