Single copper sites dispersed on hierarchically porous carbon for improving oxygen reduction reaction towards zinc-air battery

The demand for high-performance non-precious-metal electrocatalysts to replace the noble metal-based catalysts for oxygen reduction reaction(ORR)is intensively increasing.Herein,single-atomic copper sites supported on N-doped three-dimensional hierarchically porous carbon catalyst(Cu₁/NC)was prepared by coordination pyrolysis strategy.Remarkably,the Cu₁/NC-900 catalyst not only exhibits excellent ORR performance with a half-wave potential of 0.894 V(vs.RHE)in alkaline media,outperforming those of commercial Pt/C(0.851 V)and Cu nanoparticles anchored on N-doped porous carbon(CuNPs/NC-900),but also demonstrates high stability and methanol tolerance.Moreover,the Cu₁/NC-900 based Zn-air battery exhibits higher power density,rechargeability and cyclic stability than the one based on Pt/C.Both experimental and theoretical investigations demonstrated that the excellent performance of the as-obtained Cu₁/NC-900 could be attributed to the synergistic effect between copper coordinated by three N atoms active sites and the neighbouring carbon defect,resulting in elevated Cu d-band centers of Cu atoms and facilitating intermediate desorption for ORR process.This study may lead towards the development of highly efficient non-noble metal catalysts for applications in electrochemical energy conversion.     

Visible light-activated degradation of microcystin-LR by ultrathin g-C3N4 nanosheets-based heterojunction photocatalyst

Microcystins (MCs) is a harmful toxin generated by blue-green algae in water, which has seriously threatened the ecological safety of water and human body. It is urgent to develop new catalysts and techniques for the degradation of MCs. A feasible electrostatic self-assembly method was carried out to synthesize BiVO₄/g-C₃N₄ heterojunction photocatalyst with highly efficient photocatalytic ability, where BiVO₄ nanoplates with exposed {010} facets anchored to the g-C₃N₄ ultrathin nanosheets. The morphology and microstructure of the heterojunction photocatalysts were identified by XRD, SEM, TEM, XPS, and BET. The g-C₃N₄ nanosheets have huge surface area over 200 m²/g and abundant mesoporous ranging from 2-20 nm, which provides tremendous contact area for BiVO₄ nanoplates. Meanwhile, the introduction of BiVO₄ led to red-shift of the absorption spectrum of photocatalyst, which was characterized by UV-vis diffuse reflection spectroscopy (DRS). Compared with pure BiVO₄ and g-C₃N₄, the BiVO₄/g-C₃N₄ heterojunction shows a drastically enhanced photocatalytic activity in degradation of microcystin-LR (MC-LR) in water. The MC-LR could be removed within 15 minutes under the optimal ratio of BiVO₄/g-C₃N₄. The outstanding performance of the photocatalyst is attributed to synergetic effect of interface Z-scheme heterojunction and high active facets {010} of BiVO₄ nanoplates, which provides an efficient transfer pathway to separate photoinduced carriers meanwhile endows the photocatalysts with strong redox ability.     

Robust proton exchange membrane for vanadium redox flow batteries reinforced by silica-encapsulated nanocellulose

High ion selectivity and mechanical strength are critical properties for proton exchange membranes in vanadium redox flow batteries. In this work, a novel sulfonated poly(ether sulfone) hybrid membrane reinforced by core-shell structured nanocellulose (CNC-SPES) is prepared to obtain a robust and high-performance proton exchange membrane for vanadium redox flow batteries. Membrane morphology, proton conductivity, vanadium permeability and tensile strength are investigated. Single cell tests at a range of 40–140 mA cm⁻² are carried out. The performance of the sulfonated poly(ether sulfone) membrane reinforced by pristine nanocellulose (NC-SPES) and Nafion® 212 membranes are also studied for comparison. The results show that, with the incorporation of silica-encapsulated nanocellulose, the membrane exhibits outstanding mechanical strength of 54.5 MPa and high energy efficiency above 82% at 100 mA cm⁻², which is stable during 200 charge-discharge cycles.     

YSZ/MoS2 self-lubricating coating fabricated by thermal spraying and hydrothermal reaction

Thermal sprayed ceramic coatings have extensively been used in components to protect them against friction and wear. However, the poor lubricating ability severely limits their application. Herein, yttria-stabilized zirconia (YSZ)/MoS₂ composite coatings were successfully fabricated on steel substrate with the combination of thermal spraying technology and hydrothermal reaction. Results show that the synthetic MoS₂ powders are composed of numbers of ultra-thin sheets (about 7 ~ 8?nm), and the sheet has obvious lamellar structure. After vacuum impregnation and hydrothermal reaction, numbers of MoS₂ powders, look like flowers, generate inside the plasma sprayed YSZ coating. Moreover, the growing point of the MoS₂ flower is the intrinsic micro-pores of YSZ coating. The friction and wear tests under high vacuum environment indicate that the composite coating has an extremely long lifetime (>?100,000 cycles) and possesses a low friction coefficient less than 0.1, which is lower by about 0.15 times than that of YSZ coating. Meanwhile, the composite shows an extremely low wear rate (2.30?×?10^?7 mm³ N^?1 m^?1) and causes slight wear damage to the counterpart. The excellent lubricant and wear-resistant ability are attributed to the formation of MoS₂ transfer films and the ultra-smooth of the worn surfaces of hybrid coatings.     

N,N'-二(2-羟丙基)哌嗪-硫酸钠-水三元体系相平衡测定与计算

采用等温溶解平衡法测定N,N′-二(2-羟丙基)哌嗪(HPP)?Na2SO4?H2O三元体系在273.15和298.15 K下的相平衡数据，采用湿渣法测定其平衡固相数据，绘制等温相图。用改进的单组分电解质Pitzer方程计算该体系中Na2SO4和Na2SO4?10H2O的溶解平衡常数，并对相平衡数据进行理论计算。结果表明，273.15 K时存在3个结晶区，298.15 K时存在4个结晶区。HPP的存在降低了Na2SO4和Na2SO4?10H2O的相转变温度，使298.15 K下的相图中存在Na2SO4的结晶区域，且273.15和298.15 K的相图中不存在纯HPP的结晶区域。理论计算与实验数据的均方根偏差不高于0.0290，表明相平衡数据计算值与实验值较吻合，证实了改进的单组分电解质Pitzer方程适用于该体系计算。     

Synthesis of two metal-porphyrin frameworks assembled from porphyrin building motifs, 5, 10, 15, 20-tetrapyridylporphyrin and their base catalyzed property

Opening catalytically active sites in metal organic frameworks is an issue of fundamental importance for the development of effective and efficient catalysts. In this work, we first reported two metal metalloporphyrin–organic frameworks (MMPFs) with unoccupied pyridine groups as base catalysts. The reaction of Mn(II) and Co(II) with 5,10,15,20-tetrapyridylporphyrin produces two different metal metalloporphyrin–organic frameworks, {[(MnTPyP)]·H₂O}_n (MMPF-Mn) and [(CoTPyP)]_n (MMPF-Co) (TPyP = 5,10,15,20-tetrapyridylporphyrin) under hydrothermal conditions. These two MMPFs have been fully characterized by single-crystal X-ray diffraction, powder XRD, elemental analysis and thermogravimetry (TG). MMPF-Mn displays a 3D network with a nbo topology, large and open hexagonal channels, MMPF-Co reveals a 1D single zigzag chain architecture. Interestingly, both MMPFs have a high thermal stability and opening basic pyridine group, which have been tested for the base catalyzed Knoevenagel condensation reaction. The catalytic study has demonstrated that MMPF-Mn catalysts having exposed pyridine group within 1D channel displayed an excellent performance for Knoevenagel condensation reaction. When MMPF-Mn was recycled four times, its catalytic activity remained with an inconspicuous decrease. We attribute MMPF-Mn showing a better performance than MMPF-Co to its active sites being aligned in extra-large cavity with an interior diameter of 20 Å.     

Protein-based nanomaterials and nanosystems for biomedical applications: A review

Advanced protein-based nanomaterials and nanosystems (PNNS) have attracted considerable scientific interest in recent decades due to their potential in bio-applications. Nowadays, the constructed PNNS exhibit different properties for various special applications based on the characteristics of different proteins. Herein, in this review article, a systematic summary and discussion focusing on designing multi-functional PNNS are presented. The latest developments in unique synthesis strategies and detailed classification of PNNS are reviewed. The functions of proteins in PNNS for biomedical applications, such as targeting proteins, carriers, enzymes, and fluorescent indicators, are summarized. Finally, the challenges and forward-looking perspectives of PNNS research are provided.     

Effect of Supports and Promoters on the Performance of Ni-Based Catalysts in Ethanol Steam Reforming

Ethanol steam reforming (ESR) is one of the potential processes to convert ethanol into valuable products. Hydrogen produced from ESR is considered as green energy for the future and can be an excellent alternative to fossil fuels with the aim of mitigating the greenhouse gas effect. The ESR process has been well studied, using transition metals as catalysts coupled with both acidic and basic oxides as supports. Among various reported transition metals, Ni is an inexpensive material with activity comparable to that of noble metals, showing promising ethanol conversion and hydrogen yields. Additionally, different promoters and supports were utilized to enhance the hydrogen yield and the catalyst stability. This review summarizes and discusses the influences of the supports and promoters of Ni-based catalysts on the ESR process.     

Dandelion-Like Bi2S3/rGO hierarchical microspheres as high-performance anodes for potassium-ion and half/full sodium-ion batteries

Sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) have been considered as attractive alternatives for next-generation battery systems, which have promising application potential due to their earth abundance of potassium and sodium, high capacity and suitable working potential, however, the design and application of bi-functional high-performance anode still remain a great challenge up to date. Bismuth sulfide is suitable as anode owing to its unique laminar structure with relatively large interlayer distance to accommodate larger radius ions, high theoretical capacity and high volumetric capacity etc. In this study, dandelion-like Bi₂S₃/rGO hierarchical microspheres as anode material for PIBs displayed reversible capacity, and 206.91 mAh·g⁻¹ could be remained after 1,200 cycles at a current density of 100 mA·g⁻¹. When applied as anode materials for SIBs, 300 mAh·g⁻¹ could be retained after 300 cycles at 2 A·g⁻¹ and its initial Coulombic efficiency is as high as 97.43%. Even at high current density of 10 A·g⁻¹, 120.3 mAh·g⁻¹ could be preserved after 3,400 cycles. The Na₃V₂(PO₄)₃@rGO//Bi₂S₃/rGO sodium ion full cells were successfully assembled which displays stable performance after 60 cycles at 100 mA·g⁻¹. The above results demonstrate that Bi₂S₃/rGO has application potential as high performance bi-functional anode for PIBs and SIBs.