Carbon nanotube-encapsulated Co/Co3Fe7 heterojunctions as a highly-efficient bifunctional electrocatalyst for rechargeable zinc-air batteries.

In oxygen electrocatalysis, how to rationally design low-cost catalysts with reasonable structure and long-term stability is a crucial issue. Here, an in-situ growth strategy is used to construct a shaped structure encapsulating a uniformly-dispersed Co/Co3Fe7 heterojunction in nitrogen-doped carbon nanotubes (Co/Co3Fe7@NCNTs). Hollow CoFe layered-double-hydroxide prisms act as sacrifices for in-situ growth of Co/Co3Fe7 nanoparticles, which also catalyze the growth of bamboo-like NCNTs. Tubular structure not only accelerates the charge transfer through the interactions between Co and Co3Fe7, but also limits the aggregation of the particles, thereby promoting the 4e- oxygen reduction/evolution reactions (ORR/OER) kinetics and stabilizing the bifunctional activity. Co/Co3Fe7@NCNTs-800 (pyrolyzed at 800 °C) shows exceptional ORR activity (half-wave potential of 0.89 V) and methanol tolerance. Meanwhile, Co/Co3Fe7@NCNTs-800 shows a small OER overpotential of 280 mV, which increases by only 9 mV after 1000 cyclic voltammetry (CV) cycles. The outstanding bifunctionality (potential gap of 0.62 V) is ascribed to the electronic structure modulation at the Co/Co3Fe7 heterointerface. Notably, it also has a high performance as an air-cathode for rechargeable zinc-air battery, showing high power density (165 mW cm-2) and specific capacity (770.5 m Ah kg-1). This work provides a new reference for promoting the development of alloy catalysts with heterogeneous interfaces.

Modulation of Phase Transition in Cobalt Selenide with Simultaneous Construction of Heterojunctions for Highly-Efficient Oxygen Electrocatalysis in Zinc-Air Battery.

Phase transformation of cobalt selenide (CoSe2 ) can effectively modulate its intrinsic electrocatalytic activity. However, enhancing electroconductivity and catalytic activity/stability of CoSe2 still remains challenging. Heterostructure engineering may be feasible to optimize interfacial properties to promote the kinetics of oxygen electrocatalysis on a CoSe2 -based catalyst. Herein, a heterostructure consisting of CoSe2 and cobalt nitride (CoN) embedded in a hollow carbon cage is designed via a simultaneous phase/interface engineering strategy. Notably, the phase transition of orthorhombic-CoSe2 to cubic-CoSe2 (c-CoSe2 ) accompanied by in situ CoN formation is realized to build the c-CoSe2 /CoN heterointerface, which exhibits excellent/highly stable activities for oxygen reduction/evolution reactions (ORR/OER). Notably, heterostructure can modulate the local coordination environment and increase Co-Se/N bond lengths. Theoretical calculations show that Co-site (c-CoSe2 ) with an electronic state near Fermi energy level is the main active site for ORR/OER.Energetical tailoring of the d-orbital electronic structure of the Co atom of c-CoSe2 in heterostructure by in situ CoN incorporation lowers thermodynamic barriers for ORR/OER. Attractively, a zinc-air battery with a c-CoSe2 -CoN cathode displays excellent cycling stability (250 h) and charge/discharge voltage loss (0.953/0.96 V). It highlights that heterointerface engineering provides an option for modulating the bifunctional activity of metal selenides with controlled phase transformation.

CoNi Alloys Encapsulated in N-Doped Carbon Nanotubes for Stabilizing Oxygen Electrocatalysis in Zinc-Air Battery.

Alloy-based catalysts with high corrosion resistance and less self-aggregation are essential for oxygen reduction/evolution reactions (ORR/OER). Here, via an in situ growth strategy, NiCo alloy-inserted nitrogen-doped carbon nanotubes were assembled on a three-dimensional hollow nanosphere (NiCo@NCNTs/HN) using dicyandiamide. NiCo@NCNTs/HN exhibited better ORR activity (half-wave potential (E1/2) of 0.87 V) and stability (E1/2 shift of only -13 mV after 5000 cycles) than commercial Pt/C. NiCo@NCNTs/HN displayed a lower OER overpotential (330 mV) than RuO2 (390 mV). The NiCo@NCNTs/HN-assembled zinc-air battery exhibited high specific-capacity (847.01 mA h g-1) and cycling-stability (291 h). Synergies between NiCo alloys and NCNTs facilitated the charge transfer to promote 4e- ORR/OER kinetics. The carbon skeleton inhibited the corrosion of NiCo alloys from surface to subsurface, while inner cavities of CNTs confined particle growth and the aggregation of NiCo alloys to stabilize bifunctional activity. This provides a viable strategy for the design of alloy-based catalysts with confined grain-size and good structural/catalytic stabilities in oxygen electrocatalysis.

Electronic-State Modulation of Metallic Co-Assisted Co7 Fe3 Alloy Heterostructure for Highly Efficient and Stable Overall Water Splitting.

Manipulating electronic structure of alloy-based electrocatalysts can eagerly regulate its catalytic efficiency and corrosion resistance for water splitting and fundamentally understand the catalytic mechanisms for oxygen/hydrogen evolution reactions (OER/HER). Herein, the metallic Co-assisted Co7 Fe3 alloy heterojunction (Co7 Fe3 /Co) embeds in a 3D honeycomb-like graphitic carbon is purposely constructed as a bifunctional catalyst for overall water splitting. As-marked Co7 Fe3 /Co-600 displays the excellent catalytic activities in alkaline media with low overpotentials of 200 mV for OER and 68 mV for HER at 10 mA cm-2 . Theoretical calculations reveal the electronic redistribution after coupling Co with Co7 Fe3 , which likely forms the electron-rich state over interfaces and the electron-delocalized state at Co7 Fe3 alloy. This process changes the d-band center position of Co7 Fe3 /Co and optimizes the affinity of catalyst surface to intermediates, thus promoting the intrinsic OER/HER activities. For overall water splitting, the electrolyzer only requires a cell voltage of 1.50 V to achieve 10 mA cm-2 and dramatically retains 99.1% of original activity after 100 h of continuous operation. This work proposes an insight into modulation of electronic state in alloy/metal heterojunctions and explores a new path to construct more competitive electrocatalysts for overall water splitting.

A Chinese SCA36 pedigree analysis of NOP56 expansion region based on long-read sequencing.

Introduction: Spinocerebellar ataxias 36 (SCA36) is the neurodegenerative disease caused by the GGCCTG Hexanucleotide repeat expansions in NOP56, which is too long to sequence using short-read sequencing. Single molecule real time (SMRT) sequencing can sequence across disease-causing repeat expansion. We report the first long-read sequencing data across the expansion region in SCA36. Methods: We collected and described the clinical manifestations and imaging features of Han Chinese pedigree with three generations of SCA36. Also, we focused on structural variation analysis for intron 1 of the NOP56 gene by SMRT sequencing in the assembled genome. Results: The main clinical features of this pedigree are late-onset ataxia symptoms, with a presymptomatic presence of affective and sleep disorders. In addition, the results of SMRT sequencing showed the specific repeat expansion region and demonstrated that the region was not composed of single GGCCTG hexanucleotides and there were random interruptions. Discussion: We extended the phenotypic spectrum of SCA36. We applied SMRT sequencing to reveal the correlation between genotype and phenotype of SCA36. Our findings indicated that long-read sequencing is well suited to characterize known repeat expansion.

CoFe Alloy-Coupled Mo2C Wrapped by Nitrogen-Doped Carbon as Highly Active Electrocatalysts for Oxygen Reduction/Evolution Reactions.

Molybdenum carbide (Mo2C) with a Pt-like d-band electron structure exhibits certain activities for oxygen reduction and evolution reactions (ORR/OER) in alkaline solutions, but it is questioned due to its poor OER stability. Combining Mo2C with transition metals alloy is a feasible way to stabilize its electrochemical activity. Herein, CoFe-Prussian blue analogues are used as a precursor to compound with graphitic carbon nitride and Mo6+ to synthesize FeCo alloy and Mo2C co-encapsulated N-doped carbon (NG-CoFe/Mo2C). The morphology of NG-CoFe/Mo2C (800 °C) shows that CoFe/Mo2C heterojunctions are well wrapped by N-doped graphitic carbon. Carbon coating not only inhibits growth and agglomeration of Mo2C/CoFe, but also enhances corrosion resistance of NG-CoFe/Mo2C. NG-CoFe/Mo2C (800 °C) exhibits an excellent half-wave potential (E1/2 = 0.880 V) for ORR. It also obtains a lower OER overpotential (325 mV) than RuO2 due to the formation of active species (CoOOH/ß-FeOOH, as indicated by in-situ X-ray diffraction tests). E1/2 shifts only 6 mV after 5000 ORR cycles, while overpotential for OER increases only 19 mV after 1000 cycles. ORR/OER performances of NG-CoFe/Mo2C (800 °C) are close to or better than those of many recently reported catalysts. It provides an interfacial engineering strategy to enhance the intrinsic activity and stability of carbides modified by transition-metals alloy for oxygen electrocatalysis.

Highly-dispersed NiFe alloys in-situ anchored on outer surface of Co, N co­doped carbon nanotubes with enhanced stability for oxygen electrocatalysis.

Transition metal alloys have emerged as promising catalysts for oxygen reduction/evolution reactions (ORR/OER) because of their intermetallic synergy and tunable redox properties. However, for alloy nanoparticles, it is quite challenging to suppress the self-aggregation and promote the bifunctional activity. Anchoring alloys in heteroatoms-doped carbon matrix with excellent electro-conductibility is a powerful strategy to form strongly-coupled alloy-carbon nanohybrids. Here, highly-dispersed NiFe alloys are evenly in-situ anchored on the surface of Co, N co-doped carbon nanotubes (NiFe/Co-N@CNTs) via a gravity-guided chemical vapor deposition and self-assembly strategy. Stably-structured NiFe/Co-N@CNTs possesses a tubular skeleton with diameters of 80-100 nm and a hydrophilic surface. For ORR, half-wave potential of NiFe/Co-N@CNTs (0.87 V vs RHE) is higher than that of Pt/C (0.85 V). Strong synergies between NiFe alloys and Co-Nx species facilitate the charge transfer on one-dimensional conductive structure to boost the 4e- ORR kinetics. For OER, NiFe/Co-N@CNTs has a lower overpotential (300 mV) than RuO2 (400 mV) at 10 mA cm-2 due to in-situ formation of highly-active NiOOH/FeOOH species (as indicated by in-situ X-ray diffraction) at the catalytic sites on NiFe alloy. Rechargeable Zn-air battery (ZAB) with NiFe/Co-N@CNTs-based air-cathode exhibits promising open-circuit potential (1.52 V) and charge-discharge cycling stability (350 h). This alloy-carbon integrating strategy is meaningful for promoting dispersion, activity and stability of non-noble metal alloys for oxygen electrocatalysis.

Both the Complexity of Tight Junctions and Endothelial Transcytosis Are Increased During BBB Postnatal Development in Rats.

The blood-brain barrier (BBB) comprises a single layer of endothelial cells and maintains a safe and homeostatic environment for proper neuronal function and synaptic transmission. BBB is not a discrete physical barrier, but a complex, dynamic, and adaptable interface. BBB continues to mature under the influence of the neural environment within a short period of time after birth. However, the basic mechanism of BBB formation and maintenance remains a mystery. Early studies have identified two structural characteristics of microvascular endothelium: special tight junctions (TJs) and a very low transcellular vesicle transport rate. Previous studies believed that BBB damage was mainly due to the destruction of tight junctions, and the role of vesicle transcytosis was neglected, so there was a lack of research on its impact on blood-brain barrier. It is urgent to get a better clarification of the unique structural and functional characteristics of the BBB endothelium to explain the role of BBB injury in neurological diseases. RNA sequencing was used to study the molecular characterization of cerebral cortex vascular endothelium by isolating them from neonatal, adolescent and adult rats. For investigation the maintenance mechanism of the BBB, we focused on the cellular and molecular regulation of barrier formation and the two characteristics of microvascular endothelial cells. Interestingly, we found that during the development of the blood-brain barrier, although the tight junctions gradually mature, endothelial cell transcytosis is gradually enhanced, resulting in an increase in the permeability of the blood-brain barrier. This study suggested that under physiological conditions, low vesicle transport is playing an important role in maintaining the integrity of the blood-brain barrier. This study not only summarized the unique characteristics of microvascular endothelial cells, but also illustrated a clarified mechanism of the development and maintenance of BBB which can provide new therapeutic opportunities for central nervous system drug delivery. Raw data of RNA sequencing were deposited in NCBI Sequence Read Archive database (PRJNA790676).

Adult-onset autosomal dominant leukodystrophy and neuronal intranuclear inclusion disease: lessons from two new Chinese families.

INTRODUCTION: Adult-onset autosomal dominant leukodystrophy (ADLD) is a rare genetic leukoencephalopathy caused by duplication of the lamin B1 gene (LMNB1) or LMNB1 upstream deletions. Neuronal intranuclear inclusion disease (NIID) is another leukoencephalopathy due to GGC repeat expansion in the 5'-untranslated region of the NOTCH2NLC gene. Here, we report two Chinese ADLD families with neuroimaging and clinical features mimicking NIID. METHODS: We conducted detailed medical history inquiry, neurological examinations, and magnetic resonance imaging in the two families. Candidate gene sequencing and whole exome sequencing (WES) with copy number variation analysis were used to screen the genetic variations. The special points on the clinical and neuroimaging findings in the current families and differential diagnosis of ADLD with NIID are discussed. RESULTS: The two families presented with slowly progressive, multiple central nervous system symptoms, including spastic paraplegia, autonomic dysfunction, ataxia, deep sensory loss, and tremor. Clinical phenotypes were consistent within the family. Transient hypoglycemia and transient dilated pupils indicating autonomic dysfunctions were recorded for the first time in ADLD. Brain MRI showed band-like hyperintensities at the cortico-medullary junction on DWI, typical for NIID. Skin biopsy and genetic sequencing of the NOTCH2NCL gene did not support the diagnosis of NIID. Further whole exome sequencing (WES) identified the duplication mutation spanning the entire LMNB1 gene. CONCLUSIONS: The novel feature of transient hypoglycemia and dilated pupils broadens the spectrum of autonomic dysfunction in ADLD. Clinical manifestations and neuroimaging of ADLD can mimic NIID. Although ADLD is even rarer than NIID, the differential diagnosis of these two diseases should not be confused.

Recent progress of electrocatalysts for oxygen reduction in fuel cells.

Oxygen reduction reaction (ORR) has gradually been in the limelight in recent years because of its great application potential for fuel cells and rechargeable metal-air batteries. Therefore, significant issues are increasingly focused on developing effective and economical ORR electrocatalysts. This review begins with the reaction mechanisms and theoretical calculations of ORR in acidic and alkaline media. The latest reports and challenges in ORR electrocatalysis are traced. Most importantly, the latest advances in the development of ORR electrocatalysts are presented in detail, including platinum group metal (PGM), transition metal, and carbon-based electrocatalysts with various nanostructures. Furthermore, the development prospects and challenges of ORR electrocatalysts are speculated and discussed. These insights would help to formulate the design guidelines for highly-active ORR electrocatalysts and affect future research to obtain new knowledge for ORR mechanisms.

Theoretical insights into the gas/heterogeneous phase reactions of hydroxyl radicals with chlorophenols: Mechanism, kinetic and toxicity assessment.

Emission of 2-chlorophenols (2-CPs) can cause serious air pollution and health problems. Here, the reaction kinetics and products of key radicals in 2-CPs photo-oxidation are explored in both gaseous and heterogeneous reactions. Quantum chemical calculations show that •OH-addition pathways are more preferable than H-abstraction pathways in gas phase, while that is opposite in heterogeneous phase. At 298 K, the overall rate coefficients of the title reactions in gas and heterogeneous phases are 3.48 × 10-13 and 2.37 × 10-13 cm3 molecule-1 s-1 with half-lives of 55.3 h and 81.2 h, respectively. The strong H-bonds between linear Si3O2(OH)8 and 2-CPs change the energy barriers of initial •OH-addition and H-abstraction reactions, resulting in the competition between heterogeneous reactions and gas phase reactions. The products in heterogeneous reactions are chloroquinone and HONO, which can cause atmospheric acid deposition and eco-toxicity. In gas phase, self-cyclization of alkoxy radical (RO•) leads to formation of •HO2 and highly­oxygenated molecules, which cause formation of secondary organic aerosol. It is emphasized that oxidation of 2-CPs by •OH leads to formation of more toxic products for aquatic organisms. Therefore, more attention should be focused on the products originated from •OH-initiated reactions of (2-)CPs in gaseous and heterogeneous reactions.

More autosomal dominant SPG18 cases than recessive? The first AD-SPG18 pedigree in Chinese and literature review.

OBJECTIVE: Hereditary spastic paraplegia (HSP) due to ERLIN2 gene mutations was designated as spastic paraplegia 18 (SPG18). To date, SPG18 families/cases are still rarely reported. All early reported cases shared the autosomal recessive (AR) inheritance pattern. Over the past 3 years, autosomal dominant (AD) or sporadic SPG18 cases had been continuously reported. Here, we reported the clinical and genetic features of the first autosomal dominant SPG18 pedigree in Chinese. METHODS: We conducted detailed medical history inquiry, neurological examinations of the proband and his family members, and charted the family tree. The proband underwent brain and cervical magnetic resonance imaging (MRI), electromyography (EMG), and whole exome sequencing. Sanger sequencing was performed to verify the genetic variation in the proband and some family members. A literature review of all reported SPG18 families/cases was carried out to summarize the clinical-genetic characteristics of SPG18 under different inheritance patterns. RESULTS: Four patients were clinically diagnosed as chronic spastic paraplegia in three consecutive generations with the autosomal dominant inheritance model. All the patients presented juvenile-adolescent onset and gradually worsening pure HSP phenotype. Clinical phenotypes were consistent within the family. Whole exome sequencing in the proband identified a previously reported heterozygous c.502G > A (p.V168M) mutation in exon 8 of ERLIN2 gene. This mutation was cosegregated with the phenotype in the family and was classified as likely pathogenic according to American College of Medical Genetics and Genomics (ACMG) guidelines. To date, eight AR-SPG18 families, five AD-SPG18 families, and three sporadic cases had been reported. Clinical phenotype of AD-SPG18 was juvenile-adolescent onset pure HSP, while the phenotype of AR-SPG18 was mostly complicated HSP with earlier onset and more severe conditions. In rare cases, the initial spastic paraplegia could evolve to rapidly progressive amyotrophic lateral sclerosis (ALS). CONCLUSIONS: We reported the first autosomal dominant SPG18 pedigree in Chinese Han population, which added more pathogenic evidence for V168M mutation. As more SPG18 cases reported, the essentials of SPG18 need to be updated in clinical practice. Special attentions should be given in gene test for upper motor neuron disorders in case of missing heterozygous mutations in ERLIN2.

Corn Stalk-Derived Carbon Quantum Dots with Abundant Amino Groups as a Selective-Layer Modifier for Enhancing Chlorine Resistance of Membranes.

Low permeability and chlorine resistance of normal thin-film composite (TFC) membranes restrict their practical applications in many fields. This study reports the preparation of a high chlorine-resistant TFC membrane for forward osmosis (FO) by incorporating corn stalk-derived N-doped carbon quantum dots (N-CQDs) into the selective polyamide (PA) layer to construct a polydopamine (PDA) sub-layer (PTFCCQD). Membrane modification is characterized by surface morphology, hydrophilicity, Zeta potential, and roughness. Results show that TFCCQD (without PDA pretreatment) and PTFCCQD membranes possess greater negative surface charges and thinner layer-thickness (less than 68 nm). With N-CQDs and PDA pretreatment, the surface roughness of the PTFCCQD membrane decreases significantly with the co-existence of microsized balls and flocs with a dense porous structure. With the variation of concentration and type of draw solution, the PTFCCQD membrane exhibits an excellent permeability with low J(reverse salt flux)/J(water flux) values (0.1-0.25) due to the enhancement of surface hydrophilicity and the shortening of permeable paths. With 16,000 ppm·h chlorination, reverse salt flux of the PTFCCQD membrane (8.4 g m-2 h-1) is far lower than those of TFCCQD (136.2 g m-2 h-1), PTFC (127.6 g m-2 h-1), and TFC (132 g m-2 h-1) membranes in FO processes. The decline of salt rejection of the PTFCCQD membrane is only 8.2%, and the normalized salt rejection maintains 0.918 in the RO system (16,000 ppm·h chlorination). Super salt rejection is ascribed to the existence of abundant N-H bonds (N-CQDs), which are preferentially chlorinated by free chlorine to reduce the corrosion of the PA layer. The structure of the PA layer is stable during chlorination also due to the existence of various active groups grafted on the surface. This study may pave a new direction for the preparation of durable biomass-derivative (N-CQD)-modified membranes to satisfy much more possible applications.

Stable CuO with variable valence states cooperated with active Co2+ as catalyst/co-catalyst for oxygen reduction/methanol oxidation reactions.

Catalysts/co-catalysts for cathodic oxygen reduction and anodic methanol oxidation reactions (ORR/MOR) play the major roles in promoting the commercialization of direct methanol fuel cells. Herein, bimetallic zeolite-imidazolate-frameworks (CoZn-ZIFs) is used as precursor to synthesize Co3O4@NPC/CuO composites as catalysts for ORR and Pt supports/co-catalysts for MOR. The ORR activity (E1/2 = 0.83 V) and long-term stability (activity retention of 85.5% after 30,000 s) of Co3O4@NPC/CuO-400 (400 °C) dodecahedron are better than those of commercial Pt/C (10 wt%) in alkaline electrolytes. The surface CuO with variable valence states (Cu0 and Cu2+) can be used as both the active component for ORR and the protective layer for Co3O4 to enhance catalytic stability. Partial removal of CoOx from carbon framework promotes the exposure of highly active sites (Co2+) on the Co3O4. For MOR, the mass activity of Pt-Co3O4@NPC/CuO-400 (5 wt%) (1947 mA mgPt-1) is much higher than that of Pt/C (751 mA mgPt-1), mainly attributing to that the Pt active sites are uniformly dispersed on Co3O4@NPC/CuO support. The strong interaction between Pt and CuO can reduce the bond strength of Pt-CO to enhance CO resistance. Co3O4 can activate H2O molecules to provide sufficient OH- species to promote MOR. This study provides a new idea for preparation of active ORR catalysts and MOR co-catalyst from bimetallic ZIFs.

Willow Catkins-Derived Porous Carbon Membrane with Hydrophilic Property for Efficient Solar Steam Generation.

Biomass wastes are abundant and common in our daily life, and they are cost-effective, promising, and renewable. Herein, collected willow catkins were used to prepare a hydrophilic biochar composite membrane, which was placed in a tree-like evaporation configuration to simulate a natural transpiration process. The strong light absorption (∼96%) of the biochar layer could harvest light and convert it into thermal energy, which then is used to heat the surrounding water pumped by a porous water channel via capillary action. A hydrophilic light-absorber layer remarkably increased the attachment sites of water molecules, thereby maximizing the use of thermal energy. At the same time, hierarchically porous structure and large specific surface area (∼1380 m2 g-1) supplied more available channels for rapid water vapor diffusion. The as-prepared composite membrane with a low-cost advantage realized a high evaporation rate (1.65 kg m-2 h-1) only under 1 sun illumination (1 kW m-2), which was improved by roughly 27% in comparison with the unmodified hydrophobic composite membrane. The tree-like evaporation configuration with excellent heat localization resulted in the evaporator achieving a high solar-to-vapor conversion efficiency of ∼90.5%. Besides, the composite membrane could remove 99.9% sodium ions from actual seawater and 99.5% heavy metal ions from simulated wastewater, and the long-term stable evaporation performance proved its potential in actual solar desalination. This work not only fabricated an efficient evaporator but also provided a strategy for reusing various natural wastes for water purification.

Co8FeS8 wrapped in Auricularia-derived N-doped carbon with a micron-size spherical structure as an efficient cathode catalyst for strengthening charge transfer and bioelectricity generation.

The main issues regarding the practical application of microbial fuel cells (MFCs) are the poor activity and tolerance of oxygen reduction reaction (ORR) catalysts in wastewater. In this study, Auricularia chelated with Co, Fe and S ions is used as a nitrogen (N)-enriched carbon source to prepare N-doped bimetallic sulfide (Co8FeS8)-embedded carbon spheres (Co8FeS8/NSC) using a hydrothermal method. The effects of various temperatures (800-950 °C) on the structure and catalytic activity of Co8FeS8/NSC catalysts are investigated. The MFC with a Co8FeS8/NSC (900 °C) cathode obtained the maximum power density of 1.002 W m-2, which is higher than that of Pt/C (0.88 W m-2). After 1440 h of operation, the power density of the Co8FeS8/NSC (900 °C) cathode only declined by 5.49%, indicating that the Co8FeS8 activity, charge transfer and O2 transport were slightly influenced by the attached microbes and poisonous substances in the wastewater. The electrochemical results indicate that Co8FeS8/NSC (900 °C) mainly proceeds by a 4e- ORR pathway, indicating that Co8FeS8 (Co2+ and Fe2+) wrapped in NSCs (carbon spheres) can trigger synergistic effects to provide more active sites and high electrical conductivity to achieve the rapid kinetics required for the ORR. Moreover, the porous structures of the NSCs (220.97 m2 g-1) with incorporated pyridinic N, pyrrolic N and graphitic N can provide abundant available channels for O2 and OH- transport to ensure the preferential accessibility of the reactant molecules to active sites. This indicates that Auricularia-derived Co8FeS8/NSC catalysts have great potential as alternatives for precious metal-based catalysts in neutral electrolyte MFCs.

In Situ Crystallization of Active NiOOH/CoOOH Heterostructures with Hydroxide Ion Adsorption Sites on Velutipes-like CoSe/NiSe Nanorods as Catalysts for Oxygen Evolution and Cocatalysts for Methanol Oxidation.

Hydroxide ion (OH-) adsorption process is critical for accelerating the half-reactions of both metal-air batteries and direct methanol fuel cells in alkaline media. This study designs a rational catalyst/cocatalyst by constructing the readily available OH-adsorption sites to boost oxygen evolution reaction (OER) and methanol oxidation reaction (MOR). Cobalt selenide-coated nickel selenide nanorods are in situ grown on nickel foam to obtain CoSe/NiSe-nrs/NF via a one-pot solvothermal synthesis route. CoSe-0.2/NiSe-nrs/NF (Co/Ni molar ratio of 0.26) exhibits an excellent OER activity(an overpotential of 310 mV at 100 mA cm-2 and a Tafel slope of 58.3 mV dec-1). The differently oriented CoSe/NiSe-nrs with a velutipes-like structure and metallic property provide a promising electrical conductivity for charge transfer. In situ X-ray diffraction tests verify the crystallization of active ß-NiOOH during OER, and the crystallized NiOOH/CoOOH contributes to the excellent OER cycling stability in alkaline media. Synergistic effects between CoSe and NiSe-nrs/NF can balance the formation of NiOOH/CoOOH heterostructures to govern the exposure of available active sites. NiOOH/CoOOH as a highly active component can energetically adsorb OH- to promote OER. CoSe/NiSe-nrs/NFs as a low Pt-loading (0.5 wt%) support offer the mutually beneficial interactions for promoting cocatalytic and COads (poisonous intermediate) co-oxidation activities toward MOR. The electrochemically active surface area and mass activity of Pt/CoSe-0.2/NiSe-nrs/NF are 85 m2 gpt-1 and 1437.1 mA mgpt-1, respectively, which are much higher than those of commercial Pt/C (10.0 wt%). OH- absorbed on the NiOOH/CoOOH structure eliminates COads on the Pt surface via bifunctional mechanisms to improve the MOR activity. This study provides a promising reference for designing the versatile catalysts for energy conversion.

Synthesis of metallic copper modified g-C3N4 by molecular self-assembly structure and its combined catalytic performance with activated sludge.

Copper modified carbon nitride (CuCN) was prepared by a hydrothermal self-assembly reaction and following high temperature thermal polymerization process. Finally, the sample exhibits uniform one-dimensional tubular structure. Interestingly, the separation efficiency of electron-hole pair is improved, and more catalytic active sites are exposed due to the special hollow structure. Meanwhile, the presence of copper element narrows its band gap, leading to the enhancement of photocatalytic degradation performance under simulated sunlight. In addition, the effect of CuCN on dehydrogenase activity of activated sludge was determined by TTC reduction method. After adding CuCN-2, the activity of activated sludge reached 0.134 µmol g-1 min-1, which indicated that the prepared CuCN-2 had good biocompatibility. It is suitable for both photocatalytic process and activated sludge treatment process. Therefore, the combination of photocatalytic technology and activated sludge process can further completely degrade organic pollutants. We found that CuCN could protect the survival and growth of microorganisms in activated sludge, so that the degradation efficiency of CuCN to nitrobenzene could reach 94.4 %. Therefore, CuCN has broad application prospects in photocatalytic-activated sludge combined treatment.

Self-generated carbon nanotubes for protecting active sites on bifunctional Co/CoOx schottky junctions to promote oxygen reduction/evolution reactions via efficient valence transition.

Protecting active species from aggregation and corrosion may be feasible to obtain stable catalytic activities for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Herein, bamboo-shaped N-doped carbon nanotubes (hollow BS-NCNTs as shells) are self-generated to in situ wrap the Co/CoOx schottky junctions (cores) to obtain the Co/CoOx@BS-NCNTs as bifunctional ORR/OER catalysts by using the Co-chelated melamine precursor. For ORR, Co/CoOx@BS-NCNTs (700 °C) exhibits more positive peak (0.822 V vs. RHE) and half-wave (0.842 V vs. RHE) potential than those of commercial Pt/C (10 wt%). Superior ORR activity is mainly attributed to the enriched coordination-unsaturated Co2+ (tetrahedral CoTd2+) in the CoOx wrapped in the tubular structure of BS-NCNTs featuring high electrical conductivity and active N species. Moreover, the π-π bonds of CNTs are activated by N substitution, which provides a stunning electron capture and transmission capability for enhancing ORR activity. For OER, Co/CoOx@BS-NCNTs (700 °C) obtains a smaller potential (1.590 V vs. RHE) than that of RuO2/C at 10 mA cm-2. The outstanding OER activity and durability of Co/CoOx@BS-NCNTs (700 °C) originates from strong interactions between C-skeleton and Co species, and efficient Co3+/Co4+ (Co4+OOH as active sites) transition protected by the externally-grown CNTs. Furthermore, abundant oxygen vacancies on CoOx surface can facilitate the adsorption of OH-/or OER-related intermediates to improve OER activity. Therefore, this study provides a promising strategy to develop NCNTs-wrapped Co species with high catalytic activity and stability for energy conversion.

All-Solid Z-Scheme Bi-BiOCl/AgCl Heterojunction Microspheres for Improved Electron-Hole Separation and Enhanced Visible Light-Driven Photocatalytic Performance.

All-solid Z-scheme Bi-BiOCl/AgCl heterojunction microspheres are successfully prepared via hydrothermal, NaBH4 reduction and chemical deposition strategy. They are tested by various characterization methods, and they show that metal Bi is present after reduction and AgCl nanoparticles are successfully compounded onto BiOCl. Bi plays the role of a bridge connecting the two semiconductors of BiOCl and AgCl. All-solid Z-scheme heterojunction structures are formed successfully. The narrow band gap of the Z-scheme Bi-BiOCl/AgCl heterojunction microspheres is about 2.17 eV, which can expand the optical response range. Moreover, the photocatalytic hydrogen production rate still reaches 198.2 µmol h-1 g-1, extends the electron transport life, inhibits the recombination of electron hole pairs, and improves the photocatalytic activity.