Why the abnormal phenomena of D-band center theory exist?A new BASED theory for surface catalysis and chemistry

Since the D-band center theory was proposed,it has been widely used in the fields of surface chemistry by almost all researchers,due to its easy understanding,convenient operation and relative accuracy.However,with the continuous development of material systems and modification strategies,researchers have gradually found that D-band center theory is usually effective for large metal particle systems,but for small metal particle systems or semiconductors,such as single atom systems,the opposite conclusion to the D-band center theory is often obtained.To solve the issue above,here we propose a bonding and anti-bonding orbitals stable electron intensity difference(BASED)theory for surface chemistry.The newly-proposed BASED theory can not only successfully explain the abnormal phenomena of D-band center theory,but also exhibits a higher accuracy for prediction of adsorption energy and bond length of intermediates on active sites.Importantly,a new phenomenon of the spin transition state in the adsorption process is observed based on the BASED theory,where the active center atom usually yields an unstable high spin transition state to enhance its adsorption capability in the adsorption process of intermediates when their distance is about 2.5Å.In short,the BASED theory can be considered as a general principle to understand catalytic mechanism of intermediates on surfaces.

A purely green approach to low-cost mass production of zeolitic imidazolate frameworks

Although zeolitic imidazolate frameworks(ZIFs)have bright prospects in wide fields like gas storage/separation,catalysis and medicine,etc.,their large-scale applications are bottlenecked by the absence of their low-cost commercial production technique.Here,we report an uncon ventional method suitable for environmentally friendly and low-cost mass-production of ZIFs.In this method,taking the synthesis of ZIF-8 as an example,ZnO was used instead of Zn(NO_(3))_(2) in traditional solvent synthesis methods and CO_(2) was introduced to dissolve ZnO in aqueous solution of 2-methylimidazole(HMeim)and form water soluble salt([ZnMeim]^(+)[MeimCOO]^(-))at room temperature.Then,by removing CO_(2) through heating or vacuuming,Meim-ions are produced and instantaneously assemble with[ZnMeim]^(+)s to generate ZIF-8 without any by product.Due to the absence of strong acid anions(such as NO^(-)_(3) and Cl^(-) et al.)in solution,the washing of filter cake required in the conventional approaches could be omitted and the filtrate containing only water and HMeim could be reused completely.This method is really green as no waste gas or liquid generates because CO_(2) and water could be recycled perfectly.It overcomes almost all bottlenecks occurred in commercial production of ZIF-8 when using traditional methods.A pilot plant was established for mass-production of ZIF-8 and hundreds kilograms of ZIF-8 was produced,which indicates that the new method is not only environmentally friendly but also low cost and commercial accessibility.It is expected that the new method would open an avenue for commercial applications of ZIFs.

A dual metal-organic framework strategy for synthesis of FeCo@NC bifunctional oxygen catalysts for clean energy application

Developing high efficient bifunctional oxygen electrocatalysts for clean energy applications like Zin-air battery(ZAB)is highly desired,because it would reduce the cost and speed up the practical application of ZAB.Here we use a dual metal-organic framework(MOF)synthesis strategy to prepare the N-doped carbon supported bimetallic FeCo nanoparticle catalysts(marked as FeCo@NC)by pyrolysis of Zn CoZIF/MIL-101(Fe)composite.The FeCo@NC exhibits remarkable electrocatalytic activity for ORR with half-wave potential of 0.89 V vs.the reversible hydrogen electrode(RHE)and robust durability for both ORR and OER(oxygen reduction reaction and oxygen evolution reaction),which is attributed to the generation of Fe_(0.26)Co_(0.74) crystalline phase and mesopores due to the dual-MOF synthesis strategy.The rechargeable ZAB based on FeCo@NC air electrode shows a maximum energy density of139.6 mW·cm^(-2) and excellent cyclic stability over 130 h,significantly surpassing the Pt and Ir-based ZAB.The present work provides a useful dual-MOF synthesis strategy for preparing high-performance multifunctional catalysts for ORR,OER and hydrogen evolution reaction(HER).

Two-in-one strategy to construct bifunctional oxygen electrocatalysts for rechargeable Zn-air battery

Integrating two different catalytic active sites into one composite is a useful 2-in-1 strategy for designing high-efficient bifunctional catalysts,which can easily tailor the activity of each reaction.Hence,we adopt the 2-in-1 strategy to design the metal oxyhydroxide supported on N-doped porous carbons(PA-CoFe@NPC)as the oxygen bifunctional catalyst,where NPC provides the activity for oxygen reduction reaction(ORR)while the metal oxyhydroxide is responsible for oxygen evolution reaction(OER).Results demonstrate that the PA-CoFe@NPC indeed exhibits both super ORR and OER activities.Impressively,using bifunctional PA-CoFe@NPC as the oxygen electrode,the resulting Zn-air battery exhibits outstanding charge and discharge performance with the peak power density of 156.3 mW cm^(-2),and also exhibits a long-term cycle stability with continuous cyclic charge and discharge of 170 hours that is obviously better than the 20%Pt/C+IrO_(2)based one.The 2-in-1 strategy in this work can be efficiently extended to design other bi-or multi-functional electrocatalysts.

Selective adsorption of SF_(6) in covalent-and metal-organic frameworks

Sulfur hexafluoride(SF_(6))is an extremely severe greenhouse gas.It is an urgently important mission to find excellent candidates for selective adsorption of SF_(6),in order to reduce the emission of SF_(6) facilities.Here,we adopt the molecular simulation method to systematically explore the selective adsorption of SF_(6) in 22 kinds of representative covalent-and metal-organic frameworks.Results indicate that COF-6 is a promising candidate for the SF_(6) adsorption at low pressure P<20 kPa because of its small pore size,while MOF-180 and PAF-302 are excellent candidates at high pressure P=2×10^(3) kPa due to their large Brunauer-Emmett-Teller specific surface area(BET SSA)and pore volumes.For the two cases of the power industry(X_(SF_(6))=0.1)and the semiconductor industry(X_(SF_(6))=0.002)environments,COF-6 and ZIF-8 are fairly promising candidates for selective adsorption of SF_(6) from the SF_(6)/N_(2) mixtures,because they not only present the high selectivity,but also the large adsorption capacity at ambient environment,which can be considered as potential adsorbents for selective adsorption of SF_(6) at ambient conditions.

Displacement of shale gas confined in illite shale by flue gas: A molecular simulation study

The shale gas is an unconventional supplementary energy to traditional fossil energy,and is stored in layered rocks with low permeability and porosity,which leads to the difficulty for exploration of shale gas.Therefore,using CO_(2) gas to displace shale gas has become an important topic.In this work,we use molecular simulations to study the displacement of shale gas by flue gas rather than CO_(2),in which flue gas is modeled as a binary mixture of CO_(2) and N_(2) and the shale model is represented by inorganic Illite and organic methylnaphthalene.CH_(4) is used as a shale gas model.Compared to the pure CO_(2),flue gas is easily available and the cost of displacement by flue gas would become lower.Results indicate that the pore size of shale is an important factor in the process of displacing shale gas and simultaneously sequestrating flue gas,while the flue gas N_(2)-CO_(2) ratio shows a small effect on the process of CH_(4) displacement,because the high partial pressure of flue gas is the main driving force for displacement of shale gas.Moreover,the geological condition also has a significant effect on the process of CH_(4) displacement by flue gas.Therefore,we suggest that the burial depth of 1 km is suitable operation condition for shale gas displacement.It is expected that this work provides a useful guidance for exploitation of shale gas and sequestration of greenhouse gas.

Multiplicity of thermodynamic states of van der Waals gas in nanobubbles

The gas-containing nanobubbles have attracted extensive attention due to their remarkable properties and extensive application potential.However,a number of fundamental aspects of nanobubbles,including thermodynamic states for the confined gas,remain still unclear.Here we theoretically demonstrate that the van der Waals(vd W)gases confined in nanobubbles exhibit a unique thermodynamic state of remarkably deviating from the bulk gas phase,and the state transition behavior due to the sizedependent Laplace pressure.In general,the vd W gas inside nanobubbles present multiple stable or transient states,where 0–2 states are for supercritical gas and 0–4 for subcritical gas.Our further analysis based on Rayleigh–Plesset equation and free energy determination indicates that the gas states in nanobubbles exhibits different levels of stability,from which the coexistence of multiple bubble states and microphase equilibrium between droplets and bubbles are predicted.This work provides insight to understand the thermodynamic states appeared for gas in nanobubbles.

Role of substrate softness in stabilizing surface nanobubbles

The contact line pinning and supersaturation theory for the nanobubble stability has attracted extensive concerns from experimental investigators,and some experimenters argue that the contact line pinning is unnecessary.To interpret the experimental observations,we have proposed previously through molecular dynamics simulations that the deformation of soft substrates caused by surface nanobubbles may play an important role in stabilizing surface nanobubbles,while yet no quantitative theory is available for explanation of this mechanism.Here,the detailed mechanism of self-pinning-induced stability of surface nanobubbles is investigated through theoretical analysis.By manipulating substrate softness,we find that the formation of surface nanobubbles may create a deformation ridge nearby their contact lines which leads to the self-pinning effect.Theoretical analysis shows that the formation of nanobubbles on sufficiently rigid substrates or on liquid-liquid interfaces corresponds to a local free energy maximum,while that on the substrates with intermediate softness corresponds to a local minimum.Thus,the substrate softness could regulate the surface nanobubble stability.The critical condition for the self-pinning effect is determined based on contact line depinning,and the effect of gas supersaturation is explored.Finally,the approximate stability range for the surface nanobubbles is also predicted.

Assembling molybdenum-doped platinum clusters into a coral-like nanostructure for highly enhanced oxygen reduction

Regulating the electronic and geometric structures of electrocatalysts is an effective strategy to boost their catalytic properties.Herein,a coral-like nanostructure is assembled with Mo-doped Pt clusters to form a highly active catalyst toward the oxygen reduction reaction(ORR).The advantages of a Mo-doped porous skeleton,grain boundaries,and MoOx species on the Pt cluster surfaces synergistically boost the electrocatalytic performance.This unique architecture delivers 3.5-and 2.8-fold higher mass and specific activities,respectively,than commercial Pt/C.Density functional theory calculations reveal that the Mo-doped Pt clusters have an optimized Pt–O bond length of 2.110Å,which weakens the adsorption energy of the intermediate O*to yield great ORR activity.Moreover,the catalyst shows a decay in the half-wave potential of only 8 mV after 10,000 cycles of accelerated durability testing.The high stability arises from the increased dissociation energy of Pt atoms and the stable architecture of the coral-like structure of clusters.

透明硫化镍/石墨烯复合对电极用于高效染料敏化太阳能电池

对电极(counter electrode,CE)作为染料敏化太阳能电池(dye-sensitized solar cell,DSSC)的重要组成部分之一,其作用是收集外电路电子和催化还原电解质.硫化镍具有低成本和优异的电催化活性等优点,是Pt的理想替代材料.本文制备的NiS电极的透光率可以达到80%以上(600 nm处),从正面(光阳极)照射时,制备的DSSC器件光电转化效率达到7.54%,与Pt对电极的(7.48%)相当.从反面(对电极)照射时,光电转化效率达到3.96%,远高于Pt对电极(0.58%).在硫化镍电极中掺入石墨烯,可以进一步提升DSSC器件的光电转化效率,正面照射达到7.84%,反面照射达到4.59%,是正面照射效率的58.5%.电化学阻抗、循环伏安测试表明NiS对电极具有很小的串联电阻和高的电催化活性,这是其性能优于Pt的主要原因;而高的反面照射光电转化效率主要得益于NiS电极的高透光率.本文提供了一种简单、快捷、低成本的方法来制备透明、高效硫化镍对电极.

Dynamic separation of Xe and Kr by metal-organic framework and covalent-organic materials： a comparison with activated charcoal

We systematically investigate dynamic separation of Xe and Kr at room temperature using four representative porous materials(Cu-BTC, ZIF-8, COP-4 and activated carbon(AC)). Results indicate that among the four materials, Cu-BTC not only shows the highest retention volume per gram(V_g=788 m L g^(-1), which is 1.8 times of activated carbon(436 m L g^(-1))) under flowing condition, but also can separate 350 ppm Xe from 35 ppm Kr mixture in air with a high Xe/Kr selectivity of 8.6 at room temperature and 200 k Pa, due to its suitable pore morphology, open metal sites, small side pockets in the framework. Moreover, the Cu-BTC also performs well on individual separation of Xe, Kr, CO_2 from five-component gas mixture(Xe:Kr:CO_2:Ar:N_2= 1:1:1:1:0.5, V/V) and has the longest retention time for Xe(20 min) in gas chromatographic separation, suggesting that it is a good candidate for potential applications as polymeric sieves.

Polymer-based EMI shielding composites with 3D conductive networks:A mini-review

High-frequency electromagnetic waves and electronic products can bring great convenience to people’s life,but lead to a series of electromagnetic interference(EMI)problems,such as great potential dangers to the normal operation of elec-tronic components and human safety.Therefore,the research of EMI shield-ing materials has attracted extensive attention by the scholars.Among them,polymer-based EMI shielding materials with light weight,high specific strength,and stable properties have become the current mainstream.The construction of 3D conductive networks has proved to be an effective method for the prepara-tion of polymer-based EMI shielding materials with excellent shielding effective-ness(SE).In this paper,the shielding mechanism of polymer-based EMI shield-ing materials with 3D conductive networks is briefly introduced,with emphasis on the preparation methods and latest research progress of polymer-based EMI shielding materials with different 3D conductive networks.The key scientific and technical problems to be solved in the field of polymer-based EMI shielding materials are also put forward.Finally,the development trend and application prospects of polymer-based EMI shielding materials are prospected.

Fabrication of Cr-doped SrTiO3/Ti-dopedα-Fe_(2)O_(3) photoanodes with enhanced photoelectrochemical properties

Cr-doped Sr TiO_(3)/Ti-dopedα-Fe_(2)O_(3) heterojunction has been constructed by an ingenious way,i.e.using segregation titanium oxide on the surface of the Ti-dopedα-Fe_(2)O_(3) electrode to in situ prepare Cr-doped SrTiO_(3).After construction of the heterojunction,the photocurrent onset potential for water oxidation on a Ti4+dopedα-Fe_(2)O_(3) cathodically shifts by about 100 mV.Moreover,the cathodic shift of the onset potential can be preserved well even after a long time running.The results indicate the effectiveness and credibility of the fabricated heterojunction.In order to make clear the reason for the onset potential shift,the asprepared Ti-dopedα-Fe_(2)O_(3) and Cr-doped SrTiO_(3)/Ti-dopedα-Fe_(2)O_(3) samples were investigated by X-ray photoelectron spectroscopy,electrochemical impedance spectroscopy,X-ray diffraction spectroscopy,etc.Based on the experimental evidences,it is proposed that cathodic shift of the onset potential is mainly due to the enhanced charge separation at the photoanode surface.This strategy can offer a reference to construct heterojunction on other films especially for those with surface segregation.

Porous organic polymer nanotubes as luminescent probe for highly selective and sensitive detection of Fe^(3+)

Two porous organic polymer nanotubes(PNT-2 and PNT-3) were synthesized via Ni-catalyzed Yamamoto reaction, using2,4,6-tris-(4-bromo-phenyl)-[1,3,5]-triazine(TBT) as one monomer, and 2,7-dibromopyrene(DBP) or 1,3,6,8-tetrabromopyrene(TBP) as another monomer. The scanning electron microscope(SEM) images show that both PNT-2 and PNT-3 possess clear hollow tube structures. Luminescent measurements indicate that both PNT-2 and PNT-3 can serve as luminescent probe for highly selective and sensitive detection of Fe^(3+) by luminescent quenching effect. Absorption competition quenching(ACQ) mechanism is also proposed to explain luminescent quenching behavior, i.e., the overlap of the UV-spectra between Fe^(3+) and PNTs causes the energy competition, and therefore leads to luminescent quenching. Moreover, both PNT-2 and PNT-3 still show high selectivity and sensitivity for sensing Fe^(3+) in 10% ethanol aqueous solution, which means that the two porous PNTs are promising candidates as luminescent probes for detecting Fe^(3+) in practical applications.

Oxygen-Reconstituted Active Species of Single-Atom Cu Catalysts for Oxygen Reduction Reaction

Identification of an active center of catalysts under realistic working conditions of oxygen reduction reaction(ORR)still remains a great challenge and unclear.Herein,we synthesize the Cu single atom embedded on nitrogen-doped graphene-like matrix electrocatalyst(abbreviated as SA-Cu/NG).The results show that SA-Cu/NG possesses a higher ORR capability than 20%Pt/C at alkaline solution while the inferior activity to 20%Pt/C at acidic medium.Based on the experiment and simulation calculation,we identify the atomic structure of Cu-N_(2)C_(2) in SA-Cu/NG and for the first time unravels that the oxygenreconstituted Cu-N_(2)C_(2)-O structure is really the active species of alkaline ORR,while the oxygen reconstitution does not happen at acidic medium.The finding of oxygen-reconstituted active species of SA-Cu/NG at alkaline media successfully unveils the bottleneck puzzle of why the performance of ORR catalysts at alkaline solution is better than that at acidic media,which provides new physical insight into the development of new ORR catalysts.

Delaminated layered double hydroxide delivers DNA molecules as sandwich nanostructure into cells via a non-endocytic pathway

Layered double hydroxides （LDHs） are effective molecular carriers in cytological research, gene therapy, and transgenic applications. Herein, we investigated the internalization behavior of the LDH-DNA biocon- jugates via a microscopic approach and analyzed the internalization pathway by dissipative particle dynamics （DPD） simulations. We experimentally found that LDH can efficiently carry DNA into the nucleus of cell in BY-2 suspension cells. Furthermore, atomic force microscopy and X-ray diffraction anal- ysis demonstrated that the LDH-DNA bioconjugates mainly exist as a DNA-LDH-DNA sandwich complex, while the LDH-DNA-LDH sandwich complex and DNA-LDH complex cannot be excluded. The DPD simu- lations further indicated that only the DNA-LDH-DNA sandwich structure could penetrate the plasma membrane （PM）, while PM is impermeable to the LDH-DNA-LDH sandwich complex and the DNA-LDH complex. This work provides novel perspective for understanding the membrane penetration mechanism of LDH nano-sheets and new insights into the design of novel molecular delivery systems.

Label-Free DNA Sensors Based on Field-Effect Transistors with Semiconductor of Carbon Materials

Over one decade, various DNA sensors of carbon material-based field-effect transistors （FETs） have been inten- sively developed into an inspiring area of research and technology to substitute for the traditional method, for in- stance, fluorescence labeling detection. These FET DNA sensors have advantages of： directly read-out electrical signal, no need to label DNA molecule with fluorescer, high sensitivity, facility of miniaturization, simple device preparation process, high signal-to-noise ratio （SNR） and wide detection range. This review gives a comprehensive description on the state-of-the-art carbon-based FET DNA sensors from the aspect of both semiconductor material and structure of device. Several essential points in this research field, including sensitivity, selectivity, stability and challenges are addressed. Optimization of sensing performance and application of these devices are also discussed.

Pure aromatic hydrocarbons with meta-linked phenyl-core and perihedral fluorene substitutions with/without inert groups of tert-butyl： bipolar hosts for blue phosphorescence

Two pure hydrocarbon molecules of l,3,5-tris(9-phenyl-9H-fluoren-9-yl)benzene(mTPFB)and l,3,5-tris(2-tert-butyl-9-phenyl-9H-fluoren-9-yl)benzene(tBu-mTPFB)were synthesized.Due to the conjugation blocked connection mode and rigid/bulky substitutions,these two materials possess high triplet energy,enabling them as good hosts for blue phosphor in PhOLEDs.By studying their thermal,electrochemical,electronic absorption and photoluminescent properties,it was found that the influence of the inert tert-butyl group on material photoelectrical properties is negligible.For instance,mTPFB and tBu-mTPFB showed very similar absorption and emission profiles,with almost the same bandgap,triplet energy and energy levels.However,the encapsulation of tert-butyl on the 2-position of 9-phenylfluorene enhanced material thermal stability.Most importantly,carrier transport properties were improved dramatically,as proved by the mono carrier device.Blue phosphorescent OLEDs hosted by tBu-mTPFB showed external quantum efficiency of 15.2%and current efficiency of 23.0 cd/A,which were much higher than that of the OLEDs based on mTPFB with the analogous structure.

Carbon Nanofibers Encapsulated CoNiFe Bifunctional Electrocatalysts for Durable Zn-Air Batteries at Room and -40℃ Ultralow Temperatures

Reasonably designing composition and nanostructure to enhance the stability of bifunctional catalysts is highly desired for rechargeable Zn-air batteries(ZABs).Here,porous carbon nanofibers(CNFs)encapsulated CoNiFe alloy nanoparticles(NPs)(CoNiFe/CNFs)were synthesized controllably by in-situ growth and cation etching.Electrochemical tests indicated that CoNiFe/CNFs exhibited excellent bifunctional performances in both oxygen evolution reaction(OER)and oxygen reduction reaction(ORR).Using CoNiFe/CNFs as bifunctional catalysts,the assembled ZABs presented ultralong durability up to 1050 and 660 h at 5 and 25 mA cm^(-2),respectively.The assembled flexible solid-state ZABs-based polyacrylamide(PAM)hydrogel exhibited a power density of 62.9 mW cm^(-2) and 66 h durability at 2 mA cm^(-2) under ultralow temperature of -40℃.The excellent performance of CoNiFe/CNFs was ascribed to the encapsulation of CNFs by the alloy NPs and the synergy of multi-metals in the alloy NPs,because the encapsulation could suppress alloy spillage and agglomeration and protect the catalytic sites from electrolyte deterioration,thereby boosting the durability of the resulting ZABs.