Three-in-one Fe-porphyrin based hybrid nanosheets for enhanced CO_(2)reduction and evolution kinetics in Li-CO_(2)battery

Efficient cathode-catalysts with multi-functional properties are essential for Li-CO_(2)battery,while the construction of them with simultaneously enhanced CO_(2)reduction and evolution kinetics is still challenging.Here,a kind of hybrid nanosheets based on Ru nanoparticles,Fe-TAPP and grapheme oxide(GO)has been designed through a one-pot self-assembly strategy.The Ru,Fe-porphyrin and GO based hybrid nanosheets(denoted as Ru/Fe-TAPP@GO)with integrated multi-components offer characteristics of ultrathin thickness(~4 nm),high electro-redox property,uniformly dispersed morphology,and high electrical conductivity,etc.These features endow Ru/Fe-TAPP@GO with ultra-low overpotential(0.82 V)and fully reversible discharge/charge property with a high specific-capacity of 39,000 m Ah/g within 2.0-4.5 V at 100 m A/g,which are much superior to Ru@GO and Fe-TAPP@GO.The achieved performance was presented as one of the best cathode-catalysts reported to date.The synergistically enhanced activity originated from the integrated hybrid nanosheets may provide a new pathway for designing efficient cathode-catalysts for Li-CO_(2)batteries.

Cu cluster embedded porous nanofibers for high-performance CO_(2) electroreduction

Metal-doped carbon materials, as one of the most important electrocatalytic catalysts for CO_(2)reduction reaction(CO_(2)RR), have attracted increasing attention. Herein, a series of Cu cluster embedded highly porous nanofibers have been prepared through the carbonization of electro-spun MOF/PAN nanofibers.The obtained Cu cluster doped porous nanofibers possessed fibrous morphology, high porosity, conductivity, and uniformly dispersed Cu clusters, which could be applied as promising CO_(2)RR catalysts. Specifically, best of them, MCP-500 exhibited high catalytic performance for CO_(2)RR, in which the Faradaic efficiency of CO(FECO) was as high as 98% at-0.8 V and maintained above 95% after 10 h continuous electrocatalysis. The high performance might be attributed to the synergistic effect of tremendously layered graphene skeleton and uniformly dispersed Cu clusters that could largely promote the electron conductivity, mass transfer and catalytic activity during the electrocatalytic CO_(2)RR process. This attempt will provide a new idea to design highly active CO_(2)RR electrocatalyst.

Boosting CO_(2) electroreduction performance over fullerene-modified MOF-545-Co promoted by π –π interaction

Metal-organic frameworks(MOFs) have showed high promise in CO_(2)-electroreduction, yet their generally insufficient conductivity or low electron-transfer efficiency have largely restricted the wide-spread applications. Herein, fullerene molecules(i.e., C60and C70) have been successfully introduced into the pore-channels of a Co-porphyrin based MOF through a facile strategy. Thus-obtained hybrid materials present higher electron-transfer ability, enhanced CO_(2)adsorption-enthalpy and CO_(2)electroreduction activity. Notably, the charge transfer resistance(Rct) of C60@MOF-545-Co is almost 5 times lower of than that of MOF-545-Co, as well as 1.5 times increased for the CO_(2)adsorption enthalpy. As expect, the FECO of C60@MOF-545-Co(97.0%) is largely higher than MOF-545-Co(70.2%), C60@MOF-545(19.4%), C60(11.5%)and physical mixture(70.3%) and presented as one of the best CO_(2)electroreduction catalysts reported in H-cell system. The facile strategy would give rise to new insight into the exploration of powerful MOFbased hybrid materials in high-efficiency CO_(2)electroreduction.

One-step assembly of Pd-Keggin-polyoxometalates for catalytic benzothiadiazole generation and derived cell-imaging probe application

One-step assembly of organic-ligand modified Pd-Keggin-POMs has been rarely reported,so as for their applications in catalytic benzothiadiazole generation and derived cell-imaging probing.Herein,three PdKeggin-POMs(compounds 1-3)have been successfully synthesized via a one-step assembly strategy.Thus-obtained Pd-Keggin-POMs with well-defined structures and heterogeneous properties enable highly efficient catalytic benzothiadiazole generation.Specifically,compound 3 showed outstanding catalytic activities in Suzuki-Miyaura coupling reactions for the generation of benzothiadiazole derivatives(yields,90%-97%)and was represented as one of the best catalysts reported to date.Consequently,the obtained benzothiadiazoles were used as the bio-probe for tracking lipid droplets in living-cells and exhibited large Stokes shifts(130 nm),low cytotoxicity and good targeting,which could be also applied to mark the distribution of LDs in living He La cells.Systematic investigations clearly decipher the functions of PdKeggin-POMs toward finding novel bio-probe materials,highlighting a new insight into the generation of sustainable materials in life-science.

Implanting Built-In Electric Field in Heterometallic Phthalocyanine Covalent Organic Frameworks for Light-Assisted CO_(2)Electroreduction

A strategy that enables introducing bimetallic active sites is desired for the exploration of light-sensitive covalent organic framework(COF)-based electrocatalysts in light-assisted CO_(2)electroreduction.Here,salphen-pockets have been implanted into phthalocyanine(Pc)-based COFs through the elaborate design of structural struts;the produced NiPc-DFP-M COFs(M=Ni and Co)possess the advantages of controllable bimetallic centers with different coordination environments,outstanding light sensitivity,and built-in electric-field effects that can be successfully applied in light-assisted CO_(2)electroreduction.Notably,the optimal heterometallic NiPc-DFP-Co COF presents a∼100%Faradic efficiency for CO formation(FECO)in a wide potential range of−0.7 to−1.1 V and∼70%energy efficiency(−0.7 V)under light-irradiation,which is superior to mono-and homometallic COFs and under dark conditions.The high performance can be ascribed to the synergistic effect of the NiPc and Co-salphen pockets that can largely reduce the rate-determining energy-barrier and enhance the electron density to boost the light-assisted activity as supported by density functional theory calculations.A series of bimetallic Pc-based NiPc-DFP-M COF(M=Ni and Co)with integrated salphen-pockets and NiPc units have been synthesized and successfully applied in efficient light-assisted CO_(2)electroreduction.

42,573 cases of hepatectomy in China： a multicenter retrospective investigation

Hepatectomy is currently routinely performed in most hospitals in China. China owns the largest population of liver diseases and the biggest number of liver resection cases. A nationwide multicenter retrospective investigation involving 112 hospitals was performed, and focused on liver resection for patients with hepatocellular carcinoma(HCC). 42,573 cases of hepatectomy were enrolled, and 18,275 valid cases of liver resection for HCC patients were selected for statistical analysis. The epidemiology of HCC, distribution of hepatectomy, postoperative complications and prognosis were finally analyzed. In the 18,275 HCC patients,81% had hepatitis B virus infection and 10% had hepatitis C virus infection. 38% of the HCC patients had normal Alphafetoprotein(AFP) level, and other 35% had an AFP level lower than 400 ng mL^(-1). In the study period, 97% of the hepatectomy for HCC were treated with open surgery, and 23.81% had vascular exclusion techniques. The operation time was(191.7±105.6) min,the blood loss was(546.0±562.8) m L, and blood transfusion was(543.0±1,035.2) m L. The median survival for HCC patients was 631 days, with 1-, 3-, and 5-year overall survival of 73.2%, 28.8% and 19.6%, respectively. Liver cirrhosis, multiple nodules,tumor thrombosis and high AFP level were risk factors that affect postoperative survival.

Metal-Organic Frameworks Derived Porous Carbons： Syntheses, Porosity and Gas Sorption Properties

Porous carbon materials derived from metal-organic frameworks （MOFs） have been brought into stage due to the intrinsic advantages of MOFs such as high porosity and tailorable structure diversity, which might provide infinite possibility in producing porous carbons with diverse structures and various decorations. Inherited from MOFs, the porosity in carbon materials is an important factor to evaluate the performances of porous carbons （e.g. gas sorption properties, electrochemical and catalytic behaviors）. Factors that affect the porosity of porous carbon mate- rials are mainly focused on the porosity of pristine MOFs, additives and conducting conditions. However, during past decades there were still no systematical reports on the influence factors of porosity in MOFs derived porous carbon materials and corresponding gas sorption properties. In this review, we will summarize the performances of MOF-derived carbon materials （i.e. non-doped porous carbons, heteroatoms doped porous carbons, metal/metal oxide decorated porous carbons） and give a detailed discussion about the connections between the properties and four major effects （calcination temperature, loading of additional precursor, post-synthetic treatment as well as intrinsic properties of MOFs）.

Water Purification： Adsorption over Metal-Organic Frameworks

Water pollution relating to human beings＇ health is a universal problem across community society. Highly efficient, economically feasible and easily achievable approaches are long-sought-after for water purification. Adsorption processes with porous materials （e.g. zeolites, activated carbon, silica gel, metal-organic frameworks （MOFs）） have drawn much attention in this field during past decades. In it, MOFs with numerous active sites, uniform porosity and tailorable structure diversity are arising to be one of the most promising adsorbents for water purification. During the adsorption processes, influence factors that determine or affect the usability and performances of MOFs are mainly focused on the stability of MOFs, their affinity for contaminants and the conducting conditions （pH, ini- tial concentration of the contaminants）. In this review, we will systematically present the performances of MOFs （mainly focused on MOF crystals, MOF nanomaterial or MOF composites will be beyond the scope of this review） for contaminants purification （inorganic and organic contaminants） in water and give a detailed discussion about the connection among their performances, conducting condition factors and potential interaction mechanisms （e.g. electrostatic interactions, coordination or p-p interaction）. We hope this review will be beneficial to the design, regeneration and reuse of MOF adsorbents and promote the development of MOFs for water purification.

蒽醌基共价有机框架材料的一维纳米形貌自组装及其CO_(2)电还原产CH_(4)性能研究

设计形貌可调的共价有机框架(COFs)电催化剂并将其用于高选择性CO_(2)电还原反应(CO_(2)RR)是非常有研究价值和意义的.该工作设计合成了2种具有可调一维纳米形貌的AAn-COF(NF)和OH-AAn-COF(HT)材料,并通过不同时间间隔研究其不同形貌的形成机制.这类多孔纳米结构具有优异的稳定性、多孔性和CO_2吸附/活化能力等优点,将这类COFs纳米结构修饰上不同过渡金属(如Cu、Co和Zn)后,可以将其应用于CO_(2)电还原性能研究.其中,AAn-COF-Cu(NF)和OH-AAn-COF-Cu(HT)均显示出优异的CO_(2)RR性能,可以高选择性还原CO_(2)为高附加值产品CH_(4),其法拉第效率分别达77%(-128.1m Acm^(-2),-0.9V)和61%(-99.5m Acm^(-2),-1.0V).AAn-COF-Cu(NF)在较宽的电压范围(-0.8~-1.0 V)内FECH_(4)保持在53%以上,并且在-0.9 V下所达到的FECH_(4)(77%)是已报道的COFs中最高的.这种具有一维可调纳米形貌的蒽醌基COFs的制备及其CO_(2)RR应用探索,有可能为高性能CO_(2)RR电催化剂的设计提供参考.

具有类叶绿体多孔核壳结构的铋基催化剂用于高效CO2电还原

二氧化碳的过量排放引发了一系列的环境和能源问题.如何将CO2转化为我们生活所需的能源产品对于人类社会的发展具有重大意义.从能量输入和市场价值等方面考虑,利用电化学方法将CO2电还原为甲酸是一种较为理想且绿色的解决途径.本文设计合成了一系列具有类叶绿体多孔核壳结构的铋基催化剂(简写为CPBC-x)用于CO2电还原.在电催化过程中,CPBC-x外层的多孔碳可以将CO2富集并转移到催化中心Bi@Bi2O3中,Bi可以提供电子,Bi2O3可以转化为高活性的亚稳态,高效地将CO2电催化转化为甲酸.CPBC-x表现出很好的化学稳定性和优异的电催化活性,其中,CPBC-1在较宽的电位范围(-0.65^-1.0 V)内法拉第效率可以达到94%以上,其能量效率在-0.7 V下高达76.7%,是目前已报道的铋基材料中能量效率最高的.此外,这类催化剂具有良好的催化稳定性,能够保持高催化效率循环使用72 h以上.这一工作为新型CO2电还原催化剂的设计和制备提供了新思路.

Decavanadate-based Transition Metal Hybrids as Bifunctional Catalysts for Sulfide Oxidation and C-C Bond Construction

The development of bifunctional catalysts has drawn much attention in realizing efficient and feasible catalytic systems to meet the diverse dema nd of pote ntial industrial applications.Desig n of stable and powerful bifun ctional catalysts for various catalysis systems is highly desirable yet largely unmet.Here,three kinds of decavanadate-based transition metal hybrids(DTMH)(i.e.,Co-DTMH,Ni-DTMH and Ag-DTMH)have been successfully synthesized through a pH tuning strategy and further characterized.Specifically,the rare M05N six-coordinated transition metal coordination modes have been detected in Co-DTMH and Ni-DTMH,while Ag atoms in Ag-DTMH exhibited three-and five-coordinated geometries with the tuning of specially selected imidazole ligands.Thus-obtained clusters can serve as powerful bifunctional catalysts for both sulfide oxidation and C-C bond construction.Remarkably,Ag-DTMH dem on st rated excellent heteroge ne ous bifunctional catalytic properties in the selective oxidati on of sulfides and construction of C-C bond(yields up to 99%),which enable successful recycling for three cycles with remained catalytic activities and structure stability.The newly designed decavanadate-based transition metal hybrids with bifunctional property hold high promise in the practical applications like continuous catalysis or flow bed reactions.

Polyoxometalate-Induced Efficient Recycling of Waste Polyester Plastics into Metal–Organic Frameworks

Polyester plastics such as poly(ethylene terephthal-ate)(PET)are utilized commonly in everyday life,yet only a small portion of these plastics are recycled,and typically,the recycling procedures face energy or pollution problems.

Self-assembly of single metal sites embedded covalent organic frameworks into multi-dimensional nanostructures for efficient CO_(2) electroreduction

Morphology-controlled electrocatalysts with the ability of CO_(2) adsorption/activation, mass transfer, high stability and porosity are much desired in electrochemical CO_(2) reduction reaction (CO_(2)RR). Here, three kinds of multi-dimensional nanostructures (i.e., hollow sphere, nanosheets and nanofibers) have been successfully produced through the modulation of porphyrin-based covalent organic frameworks (COFs) with various modulators. The obtained nanostructures with high-stability, large surface-area, and single metal sites enable efficient CO_(2)RR into CH_(4). Notably, they all exhibit higher FE (hollow sphere, 68.2%;nanosheet, 64.2% and nanofiber, 71.0%, -0.9 V) than COF-366-Cu (43.0%, -0.9 V) after morphology control. Noteworthy, the FE of COF-366-Cu (HS) keeps higher than 52.4% over a wide potential range from -0.9 V to -1.1 V and the achieved FECH_(4) + C_(2)H_(4) (82.8%, -0.9 V) is superior to most of reported COFs and copper-based electrocatalysts. This work paves a new way in the exploration of COF-based multi-dimensional nanostructures applicable in efficient CO_(2)RR to CH_(4).

Serum N-terminal DDR1:A Novel Diagnostic Marker of Liver Fibrosis Severity

Background and Aims:The expression of discoidin domain receptor 1(DDR1)is commonly up-regulated and undergoes collagen-induced ectodomain(N-terminal)shedding during the progression of liver fibrosis.This study aimed to evaluate the clinical utility of N-terminal DDR1 as a diagnostic biomarker for liver fibrosis.Methods:N-terminal DDR1 shedding was evaluated using cell lines,liver fibrosis mouse models,clinical data of 298 patients collected from February 2019 to June 2020.The clinical data were divided into test and validation cohorts to evaluate the diagnostic performance of serum N-terminal DDR1.Results:Timeand dosage-dependent N-terminal DDR1 shedding stimulated by collagen I was observed in a hepatocyte cell line model.The type I collagen deposition and serum N-terminal DDR1 levels concurrently increased in the development of liver fibrosis in mouse models.Clinical data demonstrated a significant diagnostic power of serum N-terminal DDR1 levels as an accurate biomarker of liver fibrosis and cirrhosis.The diagnostic performance was further increased when applying N-DDR1/albumin ratio,achieving area under the curve of 0.790,0.802,0.879,and 0.865 for detecting histological fibrosis stages F≥2,F≥3,F 4 with liver biopsy as a reference method,and cirrhosis according to imaging techniques,respectively.With a cut-off of 55.6,a sensitivity,specificity,positive predictive value,and negative predictive value of 82.7%,76.6%,67.4%,and 88.3%were achieved for the detection of cirrhosis.Conclusions:Serum N-terminal DDR1 appears to be a novel diagnostic marker for liver fibrosis.