Bioinspired urchin-like murray carbon nanostructure with protection shell for advanced lithium-sulfur batteries

Commercial application of lithium-sulfur(Li-S) batteries is hindered by the insulating nature of sulfur and the dissolution of polysulfides. Here, a bioinspired 3D urchin-like N-doped Murray's carbon nanostructure(N-MCN) with interconnected micro-meso-macroporous structure and a polydopamine protection shell has been designed as an effective sulfur host for high-performance Li-S batteries. The advanced 3D hierarchically porous framework with the characteristics of the generalized Murray's law largely improves electrolyte diffusion, facilitates electrons/ions transfer and provides strong chemisorption for active species, leading to the synergistic structural and chemical confinement of polysulfides. As a result,the obtained P@S/N-MCN electrode with high areal sulfur loading demonstrates high capacity at high current densities after long cycles. This work reveals that following the generalized Murray's law is feasible to design high-performance sulfur cathode materials for potentially practical Li-S battery applications.

Advances in cathode materials for Li-O_(2)batteries

Lithium-oxygen(Li-O_(2))batteries have attracted significant attention due to their ultra-high theoretical energy density.However,serious challenges,such as potential lag,low-rate capability,round-trip efficiency,and poor cycle stability,greatly limit their practical application.This review provides a comprehensive account of the development of Li-O_(2)batteries,elucidates the current discharge/charge mechanism,and highlights both the advantages and bottlenecks of this technology.In particular,recent research progress on various cathode materials,such as carbon-based materials,noble metals,and non-noble metals,for Li-O_(2)batteries is deeply reviewed,emphasizing the impact of design strategies,material structures,chemical compositions,and microphysical parameters on oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)kinetics,as well as discharge products and overall battery performance.This review will also shed light on future research directions for oxygen electrode catalysts and material construction to facilitate the development of Li-O_(2)batteries with maximized electrochemical performance.

MoSe2 nanosheets as a functional host for lithium-sulfur batteries

Lithium-sulfur batteries(LSBs) hold great potential for large-scale electrochemical energy storage applications. Currently, the shuttle of soluble lithium polysulfide(LiPSs) intermediates with sluggish conversion kinetics and random deposition of Li2S have severely degraded the capacity, rate and cycling performances of LSBs, preventing their practical applications. In this work, ultrathin MoSe2 nanosheets with active edge sites were successfully grown on both internal and external surfaces of hollow carbon spheres with mesoporous walls(MCHS). The resulting MoSe2@MCHS composite acted as a novel functional reservoir for Li PSs with high chemical affinity and effectively mediated their fast redox conversion during charge/discharge as elucidated by experimental observations and first-principles density functional theory(DFT) calculations. The as-fabricated Li-S cells delivered high capacity, superior rate and excellent cyclability. The current work presents new insights on the delicate design and fabrication of novel functional composite electrode materials for rechargeable batteries with emerging applications.

Bronze TiO2 as a cathode host for lithium-sulfur batteries

Lithium-sulfur batteries(LSBs)are very promising for large-scale electrochemical energy storage.However,dissolution and shuttling of lithium polysulfides(LiPSs)intermediates have severely affected their overall electrochemical properties and limited their practical application.Designing polar cathode hosts that can effectively bind LiPSs and simultaneously promote their redox conversion is crucial for realizing high-performance LSBs.Herein,we report bronze TiO2(TiO2-B)nanosheets(~5 nm in thickness)chemically bonded with carbon as a novel multifunctional cathode host for advanced LSBs.Experimental observation and first-principles density functional theory(DFT)calculations reveal that the TiO2-B with exposed(100)plane and Ti^3+ions exhibited high chemical affinity toward polysulfides and effectively confined them at surface.Meantime,Ti^3+ions and interface coupling with carbon promoted electronic conductivity of the composite cathode,leading to enhanced redox conversion kinetics of LiPSs during charge/discharge.Consequently,the as-assembled TiO2-B/S cathode manifested high capacity(1165 mAh/g at 0.2 C),excellent rate capability(244 mAh/g at 5 C)and outstanding cyclability(572 mAh/g over 500cycles at 0.2 C).This work sheds insights on rational design and fabrication of novel functional electrode materials for beyond Li-ion batteries.

Enhanced stability of highly-dispersed copper catalyst supported by hierarchically porous carbon for long term selective hydrogenation

Copper based catalysts have high potential for the substituent of noble-metal based catalysts as their high selectivity and moderate activity for selective hydrogenation reaction;however,achieving further high catalytic stability is very difficult.In this work,the carbonization process of Cu-based organic frameworks was explored for the synthesis of highly-dispersed Cu supported by hierarchically porous carbon with high catalytic performance for selective hydrogenation of 1,3-butadiene.The porous hierarchy of carbon support and the dispersion of copper nanoparticles can be precisely tuned by controlling the carbonization process.The resultant catalyst carbonized at 600°C exhibits a rather low reaction temperature at 75°C for 100%butadiene conversion with 100%selectivity to butenes,due to its reasonable porous hierarchy and highly-dispersed copper sites.More importantly,unprecedentedly stability of the corresponding Cu catalyst was firstly observed for selective 1,3-butadiene hydrogenation,with both 100%butadiene conversion and 100%butenes selectivity over 120 h of reaction at 75°C.This study verifies that a simply control the carbonization process of metal organic frameworks can be an effective way to obtain Cu-based catalysts with superior catalytic performance for selective hydrogenation reaction.

Preface to Special Issue in Honor of the 80th Birthday of Professor Mingyuan He

This special issue of Chinese Journal of Catalysis is dedicated to Professor Mingyuan He on the occasion of his 80th birthday,in recognition of his distinguished contributions to many aspects in the field of catalytic science and technology.Professor He was born on February 8,1940 in Shanghai,China.In 1961,he graduated from East China Textile Engineering Institute(now Donghua University),and earned his B.S.degree in applied chemistry.He then joined the Research Institute of Petroleum Processing,SINOPEC.During 1982?1984,he worked as a visiting scholar at the Northwestern University and the University of Texas at Austin.In 2000,he became an adjunct professor at East China Normal University,and established the Shanghai Key Laboratory of Green Chemistry and Chemical Processes in 2003.

Mn^(4+) activated phosphors in photoelectric and energy conversion devices

Owing to their high luminous efficiency and tunable emission in both red light and far-red light regions,Mn^(4+)ion-activated phosphors have appealed significant interest in photoelectric and energy conversion devices such as white light emitting diode(W-LED),plant cultivation LED,and temperature thermometer.Up to now,Mn^(4+)has been widely introduced into the lattices of various inorganic hosts for brightly redemitting phosphors.However,how to correlate the structure-activity relationship between host framework,luminescence property,and photoelectric device is urgently demanded.In this review,we thoroughly summarize the recent advances of Mn^(4+)doped phosphors.Meanwhile,several strategies like co-doping and defect passivation for improving Mn^(4+)emission are also discussed.Most importantly,the relationship between the protocols for tailoring the structures of Mn^(4+)doped phosphors,increased luminescence performance,and the targeted devices with efficient photoelectric and energy conversion efficiency is deeply correlated.Finally,the challenges and perspectives of Mn^(4+)doped phosphors for practical applications are anticipated.We cordially anticipate that this review can deliver a deep comprehension of not only Mn^(4+)luminescence mechanism but also the crystal structure tailoring strategy of phosphors,so as to spur innovative thoughts in designing advanced phosphors and deepening the applications.

氯甲烷在镁修饰的ZSM-5分子筛催化剂上催化转化研究

在镁修饰的ZSM-5分子筛催化剂上,氯甲烷可以被催化转化为烃类产品。分别采用了离子交换和浸渍的方法来修饰ZSM-5分子筛。离子交换的Mg-ZSM-5催化剂和浸渍的Mg/ZSM-5催化剂都可以提高反应产物中的低碳烯烃的选择性,降低烷烃的选择性,并且保持较高的反应活性,但高的浸渍量对反应活性有一定的影响。NH3-TPD的结果表明,浸渍镁的ZSM-5催化剂的强酸中心数目明显减少。镁的修饰对催化剂酸性的影响导致了产物中低碳烯烃的增加。浸渍Mg的ZSM-5催化剂是潜在氯甲烷转化生成低碳烯烃的催化剂。

氯甲烷在H-ZS M-5催化剂上的催化转化研究

研究了氯甲烷在HZSM5分子筛催化剂上的催化转化,产物以高级烷烃和芳烃为主,其分布随反应温度而改变。在400～450℃时,催化剂上结碳量最低,而更高温度的反应产生大量的结碳并导致催化剂迅速失活。FTIR和元素分析表明,产物中的HCl对催化剂的骨架结构和组成没有明显的影响。

Recent advances in non-metal doped titania for solar-driven photocatalytic/photoelectrochemical water-splitting

Photocatalytic (PC) / Photoelectrochemical (PEC) water splitting under solar light irradiation is considered as a prospective technique to support the sustainable and renewable H_(2) economy and to reach the ultime goal of carbon neutral. TiO_(2) based photocatalysts with high chemical stability and excellent photocatalytic properties have great potential for solar-to-H_(2) conversion. To conquer the challenges of the large band-gap and rapid recombination of photo generated electron-holepairs in TiO_(2), non-metal doping turns out to be economic, facile, and effective on boosting the visible light activity. The localized defect states such as oxygen vacancy and Ti^(3+) generated by non-metal doping are located in the band-gap of TiO_(2), which result in the reduction of band-gap, thus a red-shift of the absorption edge. The hetero doping atoms such as B^(3+), I^(7+), S^(4+)/S^(6+), P^(5+) can also act as electron donors or trap sites which facilitate the charge carrier separation and suppress the recombination of electron-hole pairs. In this comprehensive review, we present the most recent advances on non-metal doped TiO_(2) photocatalysts in terms of fundamental aspects, origin of visible light activity and the PC / PEC behaviours for water splitting. In particular, the characteristics of different non-metal elements (N, C, B, S, P, Halogens) as dopants are discussed in details focusing on the synthesis approaches, characterization as well as the efficiency of PC and PEC water splitting. The present review aims at guiding the readers who want quick access to helpful information about how to efficiently improve the performance of photocatalysts by simple doping strategies and could stimulate new intuitive into the new doping strategies.

Hydrophilic bi-functional B-doped g-C_(3)N_(4) hierarchical architecture for excellent photocatalytic H_(2)O_(2) production and photoelectrochemical water splitting

Graphitic carbon nitride(g-C_(3)N_(4))has attracted great interest in photocatalysis and photoelectrocatalysis.However,their poor hydrophilicity poses a great challenge for their applications in aqueous environment.Here,we demonstrate synthesis of a hydrophilic bi-functional hierarchical architecture by the assembly of B-doped g-C_(3)N_(4)nanoplatelets.Such hierarchical B-doped g-C_(3)N_(4)material enables full utilization of their highly enhanced visible light absorption and photogenerated carrier separation in aqueous medium,leading to an excellent photocatalytic H_(2)O_(2)production rate of 4240.3μM g^(-1)h^(-1),2.84,2.64 and 2.13 times higher than that of the bulk g-C_(3)N_(4),g-C_(3)N_(4)nanoplatelets and bulk B doped g-C_(3)N_(4),respectively.Photoanodes based on these hierarchical architectures can generate an unprecedented photocurrent density of 1.72 m A cm^(-2)at 1.23 V under AM 1.5 G illumination for photoelectrochemical water splitting.This work makes a fundamental improvement towards large-scale exploitation of highly active,hydrophilic and stable metal-free g-C_(3)N_(4)photocatalysts for various practical applications.

Weaving 3D highly conductive hierarchically interconnected nanoporous web by threading MOF crystals onto multi walled carbon nanotubes for high performance Li-Se battery

Lithium-selenium(Li-Se)battery has attracted growing attention.Nevertheless,its practical application is still impeded by the shuttle effect of the formed polyselenides.Herein,we report in-situ hydrothermal weaving the three-dimensional(3 D)highly conductive hierarchically interconnected nanoporous web by threading microporous metal organic framework MIL-68(Al)crystals onto multi-walled carbon nanotubes(MWCNTs).Such 3 D hierarchically nanoporous web(3 D MIL-68(Al)@MWCNTs web)with a very high surface area,a large amount of micropores,electrical conductivity and elasticity strongly traps the soluble polyselenides during the electrochemical reaction and significantly facilitates lithium ion diffusion and electron transportation.Molecular dynamic calculation confirmed the strong affinity of MIL-68(Al)for the adsorption of polyselenides,quite suitable for Li-Se battery.Their hexahedral channels(1.56 nm)are more efficient for the confinement of polyselenides and for the diffusion of electrolytes compared to their smaller triangular channels(0.63 nm).All these excellent characteristics of 3 D MIL-68(Al)@MWCNTs web with suitable confinement of a large amount of selenium and the conductive linkage between MIL-68(Al)host by MWCNTs result in a high capacity of 453 m Ah/g at 0.2 C with 99.5%coulombic efficiency after 200 cycles with significantly improved cycle stability and rate performance.The 3 D MIL-68(Al)@MWCNTs web presents a good performance in Li-Se battery in term of the specific capacity and cycling stability and also in terms of rate performance compared with all the metal-organic framework(MOF)based or MOF derived porous carbons used in Li-Se battery.

CeO_2修饰介孔TiO_2和ZrO_2负载金催化剂催化废气中CO和挥发性有机化合物降解(英文)

Mesoporous 氧化物 TiO 2 和 ZrO 2, 经由中立 C 13(EO)6–Zr(OC3 H 7)4 集会小径，和 deposition–precipitation (DP ) 准备的修改 ceria 的 TiO 2 和 ZrO 2, 方法，展示高表面区域和一致毛孔尺寸分布被用作对金催化剂的支持。支持的金催化剂为空气污染物质的催化消退被估计，即，公司， CH 3 哦，并且(CH 3)2 O。金牌被一个 DP 方法在 mesoporous 氧化物上支持。支持和催化剂被粉末 X 光检查衍射，高分辨率的传播电子显微镜学， N 2 adsorption–desorption 分析，和规划温度的减小技术描绘。在象由 ceria 的结构、催化的性质的积极修正一样的 ceria 和 mesoporous ZrO 2 和 TiO 2 之间的 synergistic 相互作用的高度被观察。ceria 添加剂与 mesoporous 氧化物交往并且在支持的 reducibility 上导致强壮的效果。催化剂的催化行为被讨论决定修改在金 nanoparticles 和 ceria-mesoporous 氧化物支持之间的添加剂和可能的相互作用的 ceria 的角色。在修改 ceria 的 mesoporous ZrO 2 上支持的金催化剂显示了优异催化活动(在 10 °C 和 CH 3 在 60 °C 的 OH ) 。高催化的活动能被归因于支持的能力帮助氧空缺形成。研究显示修改 ceria 的 mesoporous 氧化物支持作为对基于黄金的催化剂的支持有潜力。

Self-assembly to monolayer graphene film with high electrical conductivity

Monolayer chemically converted graphene （CCG） nanosheets can be homogeneously self-assembled onto silicon wafer modified by 3-aminopr- opyl triethoxysilane （APTES） to form very thin graphene film. The CCG film was characterized by FT-IR, XRD, SEM, TEM and AFM. Results show that CCG sheets formed monolayer film after assembled onto silicon wafer and there is a very tight chemical bond between sheets and wafer. Furthermore, the electrical measurements revealed that the monolayer graphene film has an excellent electrical conductivity.

Interwoven scaffolded porous titanium oxide nanocubes/carbon nanotubes framework for high-performance sodium-ion battery

Supercapacitor-like Na-ion batteries have attracted much attention due to the high energy density of batteries and power density of capacitors.Titanium dioxide(TiO_(2)),is a promising anode material.Its performance is however seriously hindered by its low electrical conductivity and the sluggish diffusion of sodium ions(Na^(+))in the TiO_(2)matrix.Herein,this work combines porous TiO_(2)nanocubes with carbon nanotubes(CNTs)to enhance the electrical conductivity and accelerate Na^(+)diffusivity for Na-ion batteries(NIBs).In this composite,an interwoven scaffolded TiO_(2)/CNTs framework is formed to provide abundant channels and shorter diffusion pathways for electrons and ions.The in-situ X-ray diffraction and cyclic voltammetry confirm the low strain and superior transport kinetics in Na^(+)intercalation/extraction processes.In addition,the chemically bonded TiO_(2)/CNTs hybrid provides a more feasible channel for Na^(+)insertion/extraction with a much lower energy barrier.Consequently,the TiO_(2)/CNTs composite exhibits excellent electrochemical performance with a capacity of 223.4 m Ah g^(-1)at 1 C and a capacity of 142.8 m Ah g^(-1)at 10 C(3.35 A g^(-1)).The work here reveals that the combination of active materials with CNTs can largely improve the utilization efficiency and enhance their sodium storage.

Synergistic effects of carbon doping and coating of TiO_(2) with exceptional photocurrent enhancement for high performance H2 production from water splitting

The"one pot"simultaneous carbon coating and doping of TiO_(2) materials by the hydrolysis of TiCl4 in fructose is reported.The synergistic effect of carbon doping and coating of TiO_(2) to significantly boost textural,optical and electronic properties and photocurrent of TiO_(2) for high performance visible light H2 production from water splitting has been comprehensively investigated.Carbon doping can significantly increase the thermal stability,thus inhibiting the phase transformation of the Titania material from anatase to rutile while carbon coating can suppress the grain aggregation of TiO_(2).The synergy of carbon doping and coating can not only ensure an enhanced narrowing effect of the electronic band gap of TiO_(2) thus extending the absorption of photocatalysts to the visible regions,but also promote dramatically the separation of electron-hole pairs.Owing to these synergistic effects,the carbon coated and doped TiO_(2) shows much superior photocatalytic activity for both degradation of organics and photocatalytic/photoelectro chemical(PEC)water splitting under simulated sunlight illumination.The photocatalytic activity of obtained materials can reach 5,4 and 2 times higher than that of pristine TiO_(2),carbon doped TiO_(2) and carbon coated TiO_(2),respectively in the degradation of organic pollutants.The carbon coated and doped TiO_(2) materials exhibited more than 37 times and hundreds of times photocurrent enhancement under simulated sunlight and visible light,respectively compared to that of pristine TiO_(2).The present work providing new comprehensive understanding on carbon coating and doping effect could be very helpful for the development of advanced TiO_(2) materials for a large series of applications.

Three-dimensional ordered hierarchically porous carbon materials for high performance Li-Se battery

Developing host materials with high specific surface area, good electron conductivity, and fast ion transportation channel is critical for high performance lithium-selenium(Li-Se) batteries. Herein, a series of three dimensional ordered hierarchically porous carbon(3D OHPC) materials with micro/meso/macropores are designed and synthesized for Li-Se battery. The porous structure is tuned by following the concept of the generalized Murray’s law to facilitate the mass diffusion and reduce ion transport resistance.The optimized 3D Se/OHPC cathode exhibits a very high 2 nd discharge capacity of 651 m Ah/g and retains 361 m Ah/g after 200 cycles at 0.2 C. Even at a high current rate of 5 C, the battery still shows a discharge capacity as high as 155 m Ah/g. The improved electrochemical performance is attributed to the synergy effect of the interconnected and well-designed micro, meso and macroporosity while shortened ions diffusion pathways of such Murray materials accelerate its ionic and electronic conductivities leading to the enhanced electrochemical reaction. The diffusivity coefficient in Se/OHPC can reach a very high value of 1.3 × 10^(-11)cm^(2)/s, much higher than those in single pore size carbon hosts. Their effective volume expansion accommodation capability and reduced dissolution of polyselenides ensure the high stability of the battery. This work, for the first time, established the clear relationship between textural properties of cathode materials and their performance and demonstrates that the concept of the generalized Murray’s law can be used as efficient guidance for the rational design and synthesis of advanced hierarchically porous materials and the great potential of 3D OHPC materials as a practical high performance cathode material for Li-Se batteries.

Embedding tin disulfide nanoparticles in twodimensional porous carbon nanosheet interlayers for fast-charging lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries have attracted significant attention for their high specific capacity,non-toxic and harmless advantages.However,the shuttle effect limits their development.In this work,small-sized tin disulfide(SnS_(2))nanoparticles are embedded between interlayers of twodimensional porous carbon nanosheets(PCNs),forming a multi-functional nanocomposite(PCN-SnS_(2))as a cathode carrier for Li-S batteries.The graphitized carbon nanosheets improve the overall conductivity of the electrode,and the abundant pores not only facilitate ion transfer and electrolyte permeation,but also buffer the volume change during the charge and discharge process to ensure the integrity of the electrode material.More importantly,the physical confinement of PCN,as well as the strong chemical adsorption and catalytic reaction of small SnS_(2)nanoparticles,synergistically reduce the shuttle effect of polysulfides.The interaction between a porous layered structure and physical-chemical confinement gives the PCN-SnS_(2)-S electrode high electrochemical performance.Even at a high rate of 2 C,a discharge capacity of 650 mA h g^(-1)is maintained after 150 cycles,underscoring the positive results of SnS_(2)-based materials for Li-S batteries.The galvanostatic intermittent titration technique results further confirm that the PCN-SnS_(2)-S electrode has a high Li+transmission rate,which reduces the activation barrier and improves the electrochemical reaction kinetics.This work provides strong evidence that reducing the size of SnS_(2)nanostructures is beneficial for capturing and reacting with polysulfides to alleviate their shuttle effect in Li-S batteries.

Boosting reaction kinetics and shuttle effect suppression by single crystal MOF-derived N-doped ordered hierarchically porous carbon for high performance Li-Se battery

Maximizing the fixing ability of polyselenides to reduce the shuttle effect in Li-Se batteries remains highly challenging.Single crystal metal-organic framework(MOF)-derived N-doped ordered hierarchically porous carbon(SNOHPC)synthesized by a confined crystal growth and template-assisted method demonstrates excellent electrochemical performance as a host material for Li-Se battery.The large number of micropores inherited from the MOF structure provides large space and surface for Se loading and reaction sites,ensuring the high energy density of the battery.The insitu X-ray diffraction(XRD)technique is used to understand the reaction mechanism.The synergy of the interconnected three-scale-level micro-meso-macroporous structure and Ndoped polar sites can buffer the volume expansion,shorten the ion transportation with a very high diffusion coefficient of4.44×10cm^(2)sand accelerate the lithiation/delithiation reaction.Selenium is sufficiently reactive and the polyselenide intermediates are tightly fixed inside the carbon host material,thereby achieving excellent specific capacity,stability,and rate capability.Such a cathode exhibits a very high 2discharge/charge capacity of 658 and 683 mA h g,respectively,and retains a very high capacity of 367 mA h gafter 200 cycles at the current of 0.2 C.Even at the high current of 5 C,a very high discharge capacity of 230 mA h gis obtained.This work provides a new kind of high-performance porous materials with rational pore arrangement applicable for highly efficient energy storage.

Vacancy defect engineering in semiconductors for solar light‐driven environmental remediation and sustainable energy production

The introduction of vacancy defects in semiconductors has been proven to be a highly effective approach to improve their photocatalytic activity owing to their advantages of promoting light absorption,facilitating photogenerated carrier separation,optimizing electronic structure,and enabling the production of reactive radicals.Herein,we outline the state-of-the-art vacancy-engineered photocatalysts in various applications and reveal how the vacancies influence photocatalytic performance.Specifically,the types of vacancy defects,the methods for tailoring vacancies,the advanced characteri-zation techniques,the categories of photocatalysts with vacancy defects,and the corresponding photocatalytic behaviors are presented.Meanwhile,the methods of vacancies creation and the related photocatalytic performance are correlated,which can be very useful to guide the readers to quickly obtain in-depth knowledge and to have a good idea about the selection of defect engineering methods.The precise characterization of vacancy defects is highly challenging.This review describes the accurate use of a series of characterization techniques with detailed comments and suggestions.This represents the uniqueness of this comprehensive review.The challenges and development prospects in engineering photocatalysts with vacancy defects for practical applications are discussed to provide a promising research direction in this field.