Preparation of ferromagnetic binary alloy fine fibers by organic gel-thermal reduction process

Ferromagnetic metal fibers with a high aspect ratio (length/diameter) are attractive for use as high performance electromagnetic interference shielding materials. Ferromagnetic binary alloy fine fibers of iron-nickel, iron-cobalt and cobalt-nickel were prepared by the organic gel-thermal reduction process from the raw materials of critic acid and metal salts. These alloy fibers synthesized were featured with a diameter of about 1 μm and a length as long as 1 m. The structure, thermal decomposition process and morphologies of the gel precursors and fibers derived from thermal reduction of the gel precursors were characterized by FTIR, XRD, TG/DSC and SEM. The gel spinnability largely depends on the molecular structure of metal- carboxylates formed during the gel formation. The gel consisting of linear-type structural molecules shows good spinnability.

Preparation of ferromagnetic metal fine fibers by organic gel-thermal reduction process

The organic gel-thermal reduction process was used for the preparation of ferromagnetic metal Ni, Co and Fe fine fibers from the raw materials of citric acid, lactic acid and metal salts. The structure, thermal decomposition process and morphologies of the gel precursors and fibers derived from thermal reduction of these gel precursors were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, thermo-gravimetric/differential scanning calorimetry and scanning electron microscopy. The results show that spinnability of gel largely depends on molecular structure of metal-carboxylate complex that is a linear-type structure formed in the gel. As a result, the gels exhibit a good spinnability. Metal Ni, Co and Fe fine fibers are featured with diameters of around 1 μm and a high aspect ratio up to 1×106.

Metal Fe,Ni and Fe-Ni Fine Fibers Derived from the Organic Gel-Thermal Reduction Process

The organic gel-thermal reduction process was successfully used for the preparation of magnetic metal Ni, Fe, Fe-Ni fine fibers from raw materials of citric acid or lactic acid and metal salts. Ni, Fe and Fe-Ni fine fibers synthesized were featured with diameters of around 1 μm and lengths of as long as 2 m for Ni fibers, 0.5 m for iron fibers, 1 m for Fe-Ni fibers. The structure, thermal decomposition process and morphologies of the gel precursors and fibers derived from thermal reduction of these gel precursors were characterized by FTIR, XRD,TG/DSC and SEM, respectively. The gel spinnability largely depends on molecular structures of metal-carboxylate complexes formed in the gel. It is reasoned that these gels consist of linear-type structural molecules [（C6H6O7）Ni]n or [（C6H5O7）2Ni3] for the nickel citrate gel, [（C3H5O3）3Fe] for the ferric lactate gel, [（C6H5O7）5（NiFe）3] for the iron-nickel citrate gel respectively and the gels obtain showed a good spinning performance.

Quasi-Three-Dimensional Cyclotriphosphazene-Based Covalent Organic Framework Nanosheet for Efficient Oxygen Reduction

Metal-free carbon-based materials are considered as promising oxygen reduction reaction(ORR)electrocatalysts for clean energy conversion,and their highly dense and exposed carbon active sites are crucial for efficient ORR.In this work,two unique quasi-three-dimensional cyclotriphosphazene-based covalent organic frameworks(Q3CTP-COFs)and their nanosheets were successfully synthesized and applied as ORR electrocatalysts.The abundant electrophilic structure in Q3CTP-COFs induces a high density of carbon active sites,and the unique bilayer stacking of[6+3]imine-linked backbone facilitates the exposure of active carbon sites and accelerates mass diffusion during ORR.In particular,bulk Q3CTP-COFs can be easily exfoliated into thin COF nanosheets(NSs)due to the weak interlayerπ-πinteractions.Q3CTP-COF NSs exhibit highly efficient ORR catalytic activity(half-wave potential of 0.72 V vs.RHE in alkaline electrolyte),which is one of the best COF-based ORR electrocatalysts reported so far.Furthermore,Q3CTP-COF NSs can serve as a promising cathode for Zn-air batteries(delivered power density of 156 mW cm-2 at 300 mA cm^(-2)).This judicious design and accurate synthesis of such COFs with highly dense and exposed active sites and their nanosheets will promote the development of metal-free carbon-based electrocatalysts.

Metal organic polymers with dual catalytic sites for oxygen reduction and oxygen evolution reactions

Metal-organic frameworks and covalent organic frameworks have been widely employed in electrochemical catalysis owing to their designable skeletons,controllable porosities,and well-defined catalytic centers.However,the poor chemical stability and low electron conductivity limited their activity,and single-functional sites in these frameworks hindered them to show multifunctional roles in catalytic systems.Herein,we have constructed novel metal organic polymers(Co-HAT-CN and Ni-HAT-CN)with dual catalytic centers(metal-N_(4) and metal-N_(2))to catalyze oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).By using different metal centers,the catalytic activity and selectivity were well-tuned.Among them,Co-HAT-CN catalyzed the ORR in a 4e^(-)pathway,with a half-wave potential of 0.8 V versus RHE,while the Ni-HAT-CN catalyze ORR in a 2e^(-)pathway with H_(2)O_(2) selectivity over 90%.Moreover,the Co-HAT-CN delivered an overpotential of 350 mV at 10 mA cm^(-2) with a corresponding Tafel slope of 24 mV dec^(-1) for OER in a 1.0 M KOH aqueous solution.The experimental results revealed that the activities toward ORR were due to the M-N_(4) sites in the frameworks,and both M-N_(4) and M-N_(2) sites contributed to the OER.This work gives us a new platform to construct bifunctional catalysts.

Inner-pore reduction nucleation of palladium nanoparticles in highly conductive wurster-type covalent organic frameworks for efficient oxygen reduction electrocatalysis

Covalent organic frameworks(COFs)have emerged as a class of promising supports for electrocatalysis because of their advantages including good crystallinity,highly ordered pores,and structural diversity.However,their poor conductivity represents the main obstruction to their practical application.Here,we reported a novel synthesis strategy for synergistically endowing a triphenylamine-based COFs with improved electrical conductivity and excellent catalytic activity for oxygen reduction,via the in-situ redox deposition and confined growth of palladium nanoparticles inside the porous structure of COFs using reductive triphenylamine frameworks as reducing agent;meanwhile,the triphenylamine unit was oxidized to radical cation structure and affords radical cation COFs with conductivity as high as3.2*10^(-1) S m^(-1).Such a uniform confine palladium nanoparticle on highly conductive COFs makes it an efficient electrocatalyst for four-electron oxygen reduction reaction(4e-ORR),showing excellent activities and fast kinetics with a remarkable half-wave potential(E_(1/2))of 0.865 V and an ultralow Tafel slope of 39.7 mV dec^(-1) in alkaline media even in the absence of extra commercial conductive fillers.The generality of this strategy was proved by preparing the different metal and metal alloy nanoparticles supported on COFs(Au@COF,Pt@COF,AuPd@COF,AgPd@COF,and PtPd@COF)using reductive triphenylamine frameworks as reducing agent.This work not only provides a facile strategy for the fabrication of highly conductive COF supported ORR electrocatalysts,but also sheds new light on the practical application of Zn-air battery.

High-throughput mechanistic study of highly selective hydrogen-bonded organic frameworks for electrochemical nitrate reduction to ammonia

Hydrogen-bonded organic frameworks(HOFs),an emerging porous macrocyclic materials linked by hydrogen-bond,hold potential for gas separation and storage,sensors,optical,and electrocatalysts.Here,HOF-based electrocatalysts are rationally developed for nitrates reduction to ammonia,allowing not only to regulate wastewater pollution but also to accomplish carbon-neutral ammonia(NH_(3))synthesis.We preform high-throughput computational screening of thirty-six HOFs with various metals as active sites,denoted as HOF-M1,for nitrate reduction reaction(NO_(3)RR)toward NH_(3).We have implemented a hierarchical four-step screening strategy,and ultimately,HOF-Ti1 was selected based on its exceptional catalytic activity and selectivity in the NO_(3)RR process.Through additional analysis,we discovered that the d band center of the active metal sites serves as an effective parameter for designing and predicting the performance of HOFs in NO_(3)RR.This research not only showcases the immense potential of electrocatalysis in transforming NO_(3)RR into NH_(3)but also provides researchers with a compelling incentive to undertake further experimental investigations.

Ultrathin organic polymer with p-πconjugated structure for simultaneous photocatalytic disulfide bond generation and CO_(2)reduction

Combining photocatalytic organic reactions with CO_(2)reduction is an efficient solar energy utilization mode,but it is still limited by the organic species that can be matched and the low conversion.Herein,ultrathin organic polymer with p-πconjugated structure(TPP)was rationally designed and prepared,and showed a high yield of CO(15.2 mmol g^(-1))and conversion of SAS coupled products(100%),far exceeding the organic polymer with P=O structure.The enhanced photoredox activity of TPP is ascribed to the orbital interaction between the p-orbital on phosphorus and theπ-orbitals of aromatic,which can accelerate the photoinduced charge carrier separation and improve the CO_(2)adsorption capacity.TPP can also be used for the dehydrocoupling of various benzyl mercaptans to the corresponding SAS bond products.This work provides a new concept for the efficient synthesis of disulfide bonds combined with CO_(2)reduction in a photoreaction system.

Metal-organic frameworks for electrochemical reduction of carbon dioxide: The role of metal centers

Direct electrochemical reduction of CO2 into valuable chemicals and fuel is one of the most promising approaches to address the current energy crisis and lower CO2 emission.Recently,numerous metal-organic framework(MOF)and their derived materials have extensively been developed as electrocatalysts for CO2 reduction owing to their unique structure including porosity,large specific surface area,and tunable chemical structures.In this review,the recent progress of MOF-based electrocatalysts for CO2 reduction was summarized and discussed.Detailed discussions mainly focus on the synthesis and mechanism of pristine MOFs and MOF-derived materials for electrocatalytic CO2 reduction.These examples are expected to provide clues to rational design and synthesis of stable and high-performance MOFs-based electrocatalysts for CO2 reduction.

Highly efficient iron–nitrogen electrocatalyst derived from covalent organic polymer for oxygen reduction

Developing non-precious metal catalyst with high activity, good stability and low cost for electrocatalytic oxygen reduction reaction（ORR） is critical for the wide application of energy conversion system. Here, we developed a cost–effective synthetic strategy via silica assistance to obtain a novel FeC/Fe–N–C（named as COPBP-PB-Fe-900-SiO） catalyst with effective active sites of Fe–Nand FeC from the rational design two-dimensional covalent organic polymer（COPBP-PB）. The nitrogen-rich COP effectively promotes the formation of active Fe–Nsites. Additionally, the silica not only can effectively suppress the formation of large Fe-based particles in the catalysts, but also increases the degree of carbonization of the catalyst.The as-prepared COPBP-PB-Fe-900-SiOcatalyst exhibits high electrocatalytic activity for ORR with a halfwave potential of 0.85 V vs. reversible hydrogen electrode（RHE）, showing comparable activity as compared with the commercial Pt/C catalysts in alkaline media. Moreover, this catalyst also shows a high stability with a nearly constant onset potential and half-wave potential after 10,000 cycles. The present work is highly meaningful for developing ORR electrocatalysts toward wide applications.

Co-and N-doped carbon nanotubes with hierarchical pores derived from metal-organic nanotubes for oxygen reduction reaction

Biomolecules with a broad range of structure and heteroatom-containing groups offer a great opportunity for rational design of promising electrocatalysts via versatile chemistry.In this study,uniform folic acid-Co nanotubes(FA-Co NTs) were hydrothermally prepared as sacrificial templates for highly porous Co and N co-doped carbon nanotubes(Co-N/CNTs) with well-controlled size and morphology.The formation mechanism of FA-Co NTs was investigated and FA-Co-hydrazine coordination interaction together with the H-bond interaction between FA molecules was characterized to be the driving force for growth of one-dimensional nanotubes.Such distinct metal-ligand interaction afforded the resultant CNTs rich Co-N_x sites,hierarchically porous structure and Co nanoparticle-embedded conductive network,thus an overall good electrocatalytic activity for oxygen reduction.Electrochemical tests showed that Co-N/CNTs-900 promoted an efficient 4 e ORR process with an onset potential of 0.908 V vs.RHE,a limiting current density of 5.66 mA cm^(-2) at 0.6 V and a H_2 O_2 yield lower than 5%,comparable to that of 20%Pt/C catalyst.Moreover,the catalyst revealed very high stability upon continuous operation and remarkable tolerance to methanol.

Ultrathin two-dimensional metal–organic framework nanosheets for efficient electrochemical CO_(2) reduction

Electrochemical CO_(2) reduction into CO or high-value products is regarded as a feasible pathway for energy conversion,which has attracted universal attention in recent years [1-3].However,the reduction of CO_(2) molecule is a thermodynamically uphill process,which involves multiple elemental steps and the competition of hydrogen evolution reaction(HER) in aqueous solution.

Recent Progress of Metal Organic Frameworks-Based Electrocatalysts for Hydrogen Evolution,Oxygen Evolution,and Oxygen Reduction Reaction

Exploring efficient and cost-saving electrocatalysts is essential to the renewable energy storage and utilization,which is still in its embryonic period.MOFs have drawn tremendous attention due to their adjustability,abundant active sites,and plentiful pores.Notably,satisfactory electrocatalytic performance has been achieved by MOFs-based electrocatalysts comparable to traditional electrocatalysts.State-of-the-art works about the MOFs-based electrocatalysts for hydrogen evolution reaction(HER),oxygen evolution reaction(OER),and ORR were summarized in this review.This review comprises a series of modifying strategies of MOFs and their derivatives,from aspects of structure,composition,and morphology.Furthermore,the active sites and functional mechanisms’recognition are involved in this review expecting to provide reference for rationally designing efficient electrocatalysts.At last,the current status,challenges,and perspectives of MOFs-based electrocatalysts are also discussed.

Metal-organic-framework-derived formation of Co–N-doped carbon materials for efficient oxygen reduction reaction

Non-precious metal nitrogen-doped carbonaceous materials have attracted tremendous attention in the field of electrochemical energy storage and conversion.Herein,we report the designed synthesis of a novel series of Co-N-C nanocomposites and their evaluation of electrochemical properties.Novel yolkshell structured Co nanoparticles@polymer materials are fabricated from the facile coating polymer strategy on the surface of ZIF-67.After calcination in nitrogen atmosphere,the Co–N–C nanocomposites in which cobalt metal nanoparticles are embedded in the highly porous and graphitic carbon matrix are successfully achieved.The cobalt nanoparticles containing cobalt metal crystallites with an oxidized shell and/or smaller(or amorphous)cobalt-oxide deposits appear on the surface of graphitic carbons.The prepared Co–N–C nanoparticles showed favorable electrocatalytic activity for oxygen reduction reactions,which is attributed to its high graphitic degree,large surface area and the large amount existence of Co–N active sites.

Mo_(3)(C_(6)X_(6))_(2)(X=NH,S,O)monolayers:two-dimensional conductive metal-organic frameworks as effective electrocatalysts for the nitrogen reduction reaction

As a constituent element of amino acids,nitrogen plays an important role in nourishing plants,animals and other forms of life.Although the atmosphere is rich in nitrogen gas(N_(2)),the highly inert N≡N bond makes it difficult for most organisms to directly utilize N_(2).The supply of nitrogen in the biological chain mainly depends on the slow conversion of N_(2) to ammonia(NH3)by biological nitrogen fixation[1].

Nanoengineering Metal–Organic Frameworks and Derivatives for Electrosynthesis of Ammonia

Electrocatalytic synthesis under mild conditions has become increasingly important as one of the practical alternatives for industrial applications,especially for the green ammonia(NH_(3))industry.A properly engineered electrocatalyst plays a vital role in the realization of superior catalytic performance.Among various types of promising nanomaterials,metal–organic frameworks(MOFs)are competitive candidates for developing efficient electrocatalytic NH_(3) synthesis from simple nitrogen-containing molecules or ions,such as N_(2) and NO_(3)^(−).In this review,recent advances in the development of electrocatalysts derived from MOFs for the electrosynthesis of NH_(3) are collected,categorized,and discussed,including their application in the N_(2) reduction reaction(NRR)and the NO_(3)^(−)reduction reaction(NO3RR).Firstly,the fundamental principles are illustrated,such as plausible mechanisms of NH_(3) generation from N_(2) and NO_(3)^(−),the apparatus of corresponding electrocatalysis,parameters for evaluation of reaction efficiency,and detection methods of yielding NH_(3).Then,the electrocatalysts for NRR processes are discussed in detail,including pristine MOFs,MOF-hybrids,MOF-derived N-doped porous carbons,single atomic catalysts from pyrolysis of MOFs,and other MOF-related materials.Subsequently,MOF-related NO3RR processes are also listed and discussed.Finally,the existing challenges and prospects for the rational design and fabrication of electrocatalysts from MOFs for electrochemical NH_(3) synthesis are presented,such as the evolution of investigation methods with artificial intelligence,innovation in synthetic methods of MOF-related catalysts,advancement of characterization techniques,and extended electrocatalytic reactions.

Organic matter accumulation in lacustrine shale of the Permian Jimsar Sag,Junggar Basin,NW China

The lacustrine organic-rich shale in the Permian Lucaogou(LCG)Formation of the Jimsar Sag,Junggar Basin,is one of the main shale oil plays in China.In this paper,geological and geochemical research techniques were employed to evaluate the geochemical variability of the lacustrine shale and the pro-duction of organic matter and its preservation conditions.The LcG Formation is characterized by its complex mineral compositions and a wide range of organic matter richness and quality.The presence of high proportions ofβ-carotane and C2g steranes,indicates that the organic matter mainly originated from phytoplankton and aquatic algal-bacterial organisms,especially cyanobacteria.This study found that the productivity of the Lower LCG Member(P2li)was highest,and the Middle LCG Member(P_(2)l_(2))was the lowest.During the deposition of the Lower LCG Member,the lake's bottom water was predominantly a reducing environment,and the degradation of organic matter was largely a result of bacterial sulfate reduction.During the deposition of the Middle and Upper LCG members,the lake's bottom water was mainly oxidizing,and the degradation of organic matter was likely to be caused by aerobic processes.Based on a comprehensive analysis of the origin and production of organic matter,as well as its depo-sitional environment and preservation conditions,two organic matter accumulation models were pro-posed to explain the distribution of the organic-rich shale.In model A,the high influx of volcanic ash released nutrients and brought abundant sulfate into the water,the accumulation of organic matter was mainly controlled by the preservation of organic matter,which was mainly controlled by BsR.In the model B,the influx of volcanic ash was small,organic matter was mainly degraded by oxygen and the accumulation of organic matter is mainly determined by the production of organic matter.

Hydroxylated metal–organic-layer nanocages anchoring single atomic cobalt sites for robust photocatalytic CO_(2) reduction

Assembly of two-dimensional(2D)metal–organic layers(MOLs)based on the hard and soft acid–base theorem represents an exquisite strategy for the construction of photocatalytic platforms in virtue of the highly exposed active sites,much improved mass transport,and greatly elevated stability.Herein,nanocages composed of MOLs are produced for the first time through a cosolvent approach utilizing zirconium-based UiO-66-(OH)2 as the structural precursor.To endow the catalytic activity for CO_(2) conversion,single atomic Co^(2+)sites are appended to the Zr-oxo nodes of the MOL cages,demonstrating a remarkable CO yield of 7.74 mmol·g^(-1)·h^(-1) and operational stability of 97.1%product retention after five repeated cycles.Such an outstanding photocatalytic performance is mainly attributed to the unique nanocage morphology comprising enormous 2D nanosheets for augmented Co^(2+)exposure and the abundant surface hydroxyl groups for local CO_(2) enrichment.This work underlines the tailoring of both metal–organic framework(MOF)morphology and functionality to boost the turnover rate of photocatalytic CO_(2) reduction reaction(CO_(2)RR).

International Organizations’ Messages on China’s Poverty Reduction

Great Contribution to the World Antonio Guterres,UN Secretary-General The most important contribution that China is making to the eradication of poverty is Chinese achievements.The fact that China has been able to move hundreds of millions of people out of poverty and that China now has a very clear target to fully eradicate extreme poverty in China in 2020 is the most important contribution.But there is another one.

Dissimilatory Fe(Ⅲ) reduction characteristics of paddy soil extract cultures treated with glucose or fatty acids

Dissimilatory Fe(Ⅲ) reduction is a universal process with irreplaceable biological and environmental importance in anoxic environments. Our knowledge about Fe(Ⅲ) reduction predominantly comes from pure cultures of dissimilatory Fe(Ⅲ) reducing bacteria (DFRB). The objective of this study was to compare the effects of glucose and a selection of short organic acids (citrate, succinate, pyruvate, propionate, acetate, and formate) on Fe(Ⅲ) reduction via the anaerobic culture of three paddy soil solutions with Fe...