Interfacial Modification of NiO_(x)by Self-assembled Monolayer for Efficient and Stable Inverted Perovskite Solar Cells

NiO_(x)as a hole transport material for inverted perovskite solar cells has received great attention owing to its high transparency,low fabrication temperature,and superior stability.However,the mismatched energy levels and possible redox reactions at the NiO_(x)/perovskite interface severely limit the performance of NiO_(x) based inverted perovskite solar cells.Herein,we introduce a p-type self-assembled monolayer between NiO_(x)and perovskite layers to modify the interface and block the undesirable redox reaction between perovskite and NiO_(x)The selfassembled monolayer molecules all contain phosphoric acid function groups,which can be anchored onto the NiOr surface and passivate the surface defect.Moreover,the introduction of self-assembled monolayers can regulate the energy level structure of NiO_(x),reduce the interfacial band energy offset,and hence promote the hole transport from perovskite to NiO_(x)layer.Consequently,the device performance is significantly enhanced in terms of both power conversion efficiency and stability.

Nanoheterostructured photocatalysts for improving photocatalytic hydrogen production

Rapid industrialization has accordingly increased the demand for energy.This has resulted in the increasingly severe energy and environmental crises.Hydrogen production,based on the photocatalytic water splitting driven by sunlight,is able to directly convert solar energy into a usable or storable energy resource,which is considered to be an ideal alternative energy source to assist in solving the energy crisis and environmental pollution.Unfortunately,the hydrogen production efficiency of single phase photocatalysts is too low to meet the practical requirements.The construction of heterostructured photocatalyst systems,which are comprised of multiple components or multiple phases,is an efficient method to facilitate the separation of electron‐hole pairs to minimize the energy‐waste,provide more electrons,enhance their redox ability,and hence improve the photocatalytic activity.We summarize the recent progress in the rational design and fabrication of nanoheterostructured photocatalysts.The heterojunction photocatalytic hydrogen generation systems can be divided into type‐I,type‐II,pn‐junction and Z‐scheme junction,according to the differences in the transfer of the photogenerated electrons and holes.Finally,a summary and some of the challenges and prospects for the future development of heterojunction photocatalytic systems are discussed.

Vesicle-shaped ZIF-8 shell shielded in 3D carbon cloth for uniform nucleation and growth towards long-life lithium metal anode

Lithium metal has aroused extensive research interests as the anode for next-generation rechargeable batteries.However,the well-known dendritic Li growth and consequent safety issues still impair the long-term cycling performance.Herein,a hybrid structure composed of 3 D carbon cloth and vesicleshaped hollow ZIF-8 modification shell(HZS@CC)was prepared as a smart host for guiding uniform Li deposition.The long-range interconnected 3 D carbon fiber network enables the reduced local current density with homogeneous electrons distribution.Synergistically,abundant surface polar groups and the ultrastructure on ZIF-8 particles effectively guide a well-distributed Li-ions flow to promote the uniform Li nucleation and growth.As a result,stable Li plating/stripping for 2000 h with a low overpotential(≈15 mV)at 1 mA cm^(-2) were achieved in symmetric cells.Coupling with LiFePO_(4) cathode,the full cell delivered long life over 1200 cycles at 6 C.This research demonstrated that a homogenization guiding of Li-ions is of great importance to better make use of the structural advantage of 3 D hosts and achieve improved electrochemical performance.

Rational screening of metal coating on Zn anode for ultrahigh-cumulative-capacity aqueous zinc metal batteries

Aqueous zinc metal batteries feature intrinsic safety,but suffer from severe dendrite growth and water-derived side reactions.Many metal coatings have been explored for stabilizing Zn metal anode via a trialand-error approach.Here,we propose an exercisable way to screen the potential metal coating on Zn anodes in view of de-polarization effect and dendrite-suppressing ability theoretically.As an output of this screening,cadmium(Cd) metal is checked experimentally.Therefore,symmetric ZnllZn cells using Cd coated Zn(Zn@Cd) exhibit an ultra-long cycle life of 3500 h(nearly 5 months) at a high current density of 10 mA cm^(-2),achieving a record-high cumulative capacity(35 A h cm^(-2)) compared to the previous reports.The full cells of Zn@Cd‖MnO_(2) display a markedly improved cycling performance under harsh conditions including a limited Zn supply(N/P ratio=1.7) and a high areal capacity(3.5 mA h cm^(-2)).The significance of this work lies in not only the first report of Cd coating for stabilizing Zn metal anode,but also a feasible way to screen the promising metal materials for other metal anodes.

Recent progress and perspectives on Sb_(2)Se_(3)-based photocathodes for solar hydrogen production via photoelectrochemical water splitting

Photoelectrochemical(PEC) cells involved with semiconductor electrodes can simultaneously absorb solar energy and perform chemical reactions, which are considered as an attractive strategy to produce renewable and clean hydrogen energy. Sb_(2)Se_(3) has been widely investigated in constructing PEC photocathodes benefitting of its low toxicity, suitable band gap, superior optoelectronic properties, and outstanding photocorrosion stability. We first present a brief overview of basic concepts and principles of PEC water splitting as well as a comparison between Sb_(2)Se_(3) and other numerous candidates. Then the material characteristics and preparation methods of Sb_(2)Se_(3) are introduced. The development of Sb_(2)Se_(3)-based photocathodes in PEC water splitting with various architectures and engineering efforts(i.e., absorber engineering, interfaces engineering, co-catalyst engineering and tandem engineering) to improve solar-to-hydrogen(STH) efficiency are highlighted. Finally, we debate the possible future directions to further explore the researching fields of Sb_(2)Se_(3)-based photocathodes with a strongly positive outlook in PEC processed solar hydrogen production.

Self-supported Ni2P nanosheets on low-cost three-dimensional Fe foam as a novel electrocatalyst for efficient water oxidation

Electrochemical water splitting into hydrogen and oxygen is a promising strategy for future renewable energy conversion devices.The oxygen evolution reaction(OER)is considered as the bottleneck reaction in an overall water splitting system because it involves 4e- and 4H+ transfer processes.Currently,it is highly desirable to explore low-cost alternative catalysts for OER at ambient conditions.Herein,we report for the first time that nickel phosphide(Ni2P)nanosheets can be facilely grown on Fe foam(FF)as an efficient electrocatalyst for OER with excellent durability and catalytic activity under alkaline conditions.To reach a current density of 10 m A/cm2,the Ni2P-FF catalyst required a low overpotential of only 198 mV for OER.The catalyst’s high OER activity and durability were well maintained at a high current density.The required overpotentials were only 267 and 313 mV to achieve the current densities of 100 and 300 m A/cm2,respectively.The combination of low-cost Fe foam with Ni2P provides a promising low-cost catalyst for large-scale application of electrocatalytic water splitting.

Bifunctional TiO2 Catalysts for Efficient Cr（VI） Photoreduction Under Solar Light Irradiation Without Addition of Acids

Bifunctional TiO2 photocatalysts co-doped with nitrogen and sulfur were prepared by the controlled thermal decomposition of ammonium titanyl sulfate precursor. They have both photocatalytic activity and Brφnsted acidity, and thus are active in the photoreduction of Cr（VI） under solar light irradiation without the addition of acids. The activity is superior to that of Degussa P25 in the acidified suspension at the same pH adjusted by H2SO4.

Nitrogen and fluorine co-doped TiO_(2)/carbon microspheres for advanced anodes in sodium-ion batteries: High volumetric capacity, superior power density and large areal capacity

Fast charging and high volumetric capacity are two of the critical demands for sodium-ion batteries(SIBs).Although nanostructured materials achieve outstanding rate performance,they suffer from low tap density and small volumetric capacity.Therefore,how to realize large volumetric capacity and high tap density simultaneously is very challenging.Here,N/F co-doped TiO_(2)/carbon microspheres(NF- TiO_(2)/C)are synthesized to achieve both of them.Theoretical calculations reveal that N and F co-doping increases the contents of oxygen vacancies and narrows the bandgaps of TiO_(2) and C,improving the electronic conductivity of NF- TiO_(2)/C.Furthermore,NF- TiO_(2)/C exhibits the high binding energy and low diffusion energy barrier of Na+,significantly facilitating Na+storage and Na+diffusion.Therefore,NF- TiO_(2)/C offers a high tap density(1.51 g cm^(-3)),an outstanding rate performance(125.9 mAh g^(-1) at 100 C),a large volumetric capacity(190 mAh cm^(-3) at 100 C),a high areal capacity(4.8 mAh cm^(-2))and an ultra-long cycling performance(80.2%after 10,000 cycles at 10 C)simultaneously.In addition,NF- TiO_(2)/C||Na_(3)V_(2)(PO_(4))_(3) full cells achieve an ultrahigh power density of 25.2 kW kg^(-1).These results indicate the great promise of NF- TiO_(2)/C as a high-volumetric-capacity and high-power-density anode material of SIBs.

Integrating noble-metal-free NiS cocatalyst with a semiconductor heterojunction composite for efficient photocatalytic H_2 production in water under visible light

Photocatalytic water splitting is an economical and sustainable pathway to use solar energy for large‐scale H2production.We report a highly efficient noble‐metal‐free photocatalyst formed by integrating amorphous NiS with a CdS nanorods(NRs)/ZnS heterojunction material for photocatalytic H2production in water under visible light irradiation(?>420nm).The results show that the photocatalytic H2production rate reaches an optimal value of up to574μmol·h–1after the loading of NiS,which is more than38times higher than the catalytic activity of pure CdS NRs.The average apparent quantum yield is^43.2%during5h of irradiation by monochromatic420nm light.The present study demonstrates the advantage of integration strategies to form not only semiconductor heterojunctions but also photocatalyst‐cocatalyst interfaces to enhance the catalytic activity for photocatalytic H2production.

Graft Copolymerization of N,N-Dimethylacrylamide to Cellulose in Homogeneous Media Using Atom Transfer Radical Polymerization for Hemocompatibility

In homogeneous media, N,N-Dimethylacrylamide (DMA) was grafted copolymerization to cellulose by a metal-catalyzed atom transfer radical polymerization (ATRP) process. First, cellulose was dissolved in DMAc/LiCl system, and it reacted with 2-bromoisobutyloyl bromide (BiBBr) to produce macroinitiator (cell-BiB). Then DMA was polymerized to the cellulose backbone in a homogeneous DMSO solution in presence of the cell-BiB. Characterization with FT-IR, NMR, and GPC measurements showed that there obtained a graft copolymer with cellulose backbone and PDMA side chains (cell-PDMA) in well-defined structure. The proteins adsorption studies showed that the cellulose membranes modified by the as-prepared cell-PDMA copolymer owns good protein adsorption resistancet.

Selection rules for electric multipole transition of triatomic molecule in scattering experiments

In the electron or x-ray scattering experiment,the measured spectra at larger momentum transfer are dominated by the electric dipole-forbidden transitions,while the corresponding selection rules for triatomic molecules have not been clearly elucidated.In this work,based on the molecular point group,the selection rules for the electric multipolarities of the electronic transitions of triatomic molecules are derived and summarized into several tables with the variation of molecular geometry in the transition process being considered.Based on the summarized selection rules,the electron energy loss spectra of H2O,CO2,and N2O are identified,and the momentum transfer dependence behaviors of their valence-shell excitations are explained.

Tuning electrochemical transformation process of zeolitic imidazolate framework for efficient water oxidation activity

Metal-organic frameworks(MOFs)have been widely studied as efficient electrocatalysts for water oxidation due to their tunable structure and easy preparation.However,the rational design of MOFs-based electrocatalysts and fundamental understanding of their structural evolution during oxygen evolution reaction(OER)remain critical challenges.Here,we report a facile approach to tune the structural transformation process of the Co-based zeolitic imidazolate framework(ZIF)during the OER process by using water molecules as a vacancy promoter.The modified ZIF catalyst accelerates the structural transformation from MOF precursor to electrochemical active species and simultaneously enhances the vacancy density during the electrochemical activation process.The optimized electrocatalyst exhibits an extremely low overpotential 175 mV to deliver 10 mA cm^(-2) and superior durability(100 h)at 100 mA cm^(-2).The comprehensive characterization results reveal the structural transformation from the initial tetrahedral Co sites to cobalt oxyhydroxide(CoOOH)and the formation process of oxygen vacancies(CoOOH-Vo)at a high anodic potential.These findings represent a promising way to achieve highly active MOF-based electrocatalysts for water oxidation.

Formation and Growth of Silver Nanocubes upon Nanosecond Pulsed Laser Irradiation: Effects of Laser Intensity and Irradiation Time

Silver nanoparticles (AgNPs) were fabricated by repetitive irradiation of near ultraviolet (UV) nanosecond laser pulses (355 nm, 5 ns) in an aqueous solution of silver nitrate in the absence of stabilizing agents. A broad absorption peak was observed in the visible region showing the formation of a variety of AgNPs in the solution. Among the variety of products, it was found that silver nanocubes (AgNCs) grew in size with longer laser irradiation time. The size of AgNCs also increased with higher laser intensity. The average size of AgNCs, investigated by a scanning electron microscope (SEM) was in the range of 75 - 200 nm. The number of reduced atoms in AgNCs as a function of laser intensity showed that the AgNCs are apparently produced by a four photon process, implying that the formation of dimer silver atoms is essential for the formation.

“Buckets effect”in the kinetics of electrocatalytic reactions

In this study,we systematically investigated the effect of proton concentration on the kinetics of the oxygen reduction reaction(ORR)on Pt(111)in acidic solutions.Experimental results demonstrate a rectangular hyperbolic relationship,i.e.,the ORR current excluding the effect of other variables increases with proton concentration and then tends to a constant value.We consider that this is caused by the limitation of ORR kinetics by the trace oxygen concentration in the solution,which determines the upper limit of ORR kinetics.A model of effective concentration is further proposed for rectangular hyperbolic relationships:when the reactant concentration is high enough to reach a critical saturation concentration,the effective reactant concentration will become a constant value.This could be due to the limited concentration of a certain reactant for reactions involving more than one reactant or the limited number of active sites available on the catalyst.Our study provides new insights into the kinetics of electrocatalytic reactions,and it is important for the proper evaluation of catalyst activity and the study of structureperformance relationships.

Optically Forbidden Excitations of 2s Electron of Neon Studied by Fast Electron Impact

The electron energy loss spectrum in the energy region of 42-48.5 eV of neon is measured with an angle-resolved fast-electron energy-loss spectrometer at an incident electron energy of 2500eV. Besides the dipole-allowed autoionization transitions of 2s^-1ap （n -= 3, 4） and 2p^-23s3p, the dipole-forbidden ones of 2s^-1ns （n = 3 - 6） and 2s^-13d are observed. The line profile parameters, i.e. Er, F and q for these transitions, are determined, and the momentum transfer dependence behaviour is discussed.

Bell Theorem without Inequality for Some Generalized GHZ and W States

Bell＇s theorem without inequalities is applied for some general Greenberger-Horn-Zeilinger （GHZ） states and W states and a wide range of such states can exhibit all-versus-nothing conflict between local realism and quantum theory. The case of standard GHZ state is contained in our proposal. For some generalized GHZ states more intensive violation on local realism is manifested.

Electrolyte additive enhances the electrochemical performance of Cu for rechargeable Cu//Zn batteries

Cu-based cathodes in aqueous batteries become very attractive in view of high theoretical capacity,moderate operation voltage and rich reserves of raw materials.However,their applications are obstructed by serious side reactions.The side reaction mainly arises from the spontaneous formation of Cu_(2)O,which occupies the electrode surface and lowers the reaction reversibility.Here,Na_(2)EDTA is introduced to address these issues.Both experimental results and theoretical calculations indicate that the Na_(2)EDTA reshapes the solvation structure of Cu^(2+)and modifies the electrode/electrolyte interface.Therefore,the redox potential of Cu^(2+)/Cu_(2)O is reduced and the surface of Cu is protected from H2O,thereby inhibiting the formation of Cu_(2)O.Meanwhile,the change in the solvation structure reduces the electrostatic repulsion between Cu^(2+)and the cathode,leading to high local concentration and benefiting uniform deposition.The results shed light on the applications of rechargeable Cu-based batteries.

MnHCF/MnO_2 Core-shell Nanostructures as Cathode Material for Supercapacitors with High Energy Density

A nanocomposite of manganese dioxide coated manganese hexacyanoferrate was synthesized by a facile co-precipitation method and tested as active electrode material for an electrochemical supercapacitor. A way called "Deep electro-oxidation" was used to generate manganese dioxide coated layer for stabilizing the electrode material. The structure and ingredient of the resulting MnHCF/MnO2 composites were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and X-ray Photoelectron Spectroscopy. Electrochemical testing showed a capacitance of 225.6 F/g at a sweep rate of 5 mV/s within a voltage range of 1.3 V, and high energy density of 37.2 Wh/kg at a current density of 0.5 A/g in galvanostatic charge/discharge cycling. It is suggested that the two different components, manganese hexacyanoferrate core and manganese dioxide shell, lead to an integrated electrochemical behavior, and an enhanced capacitor. The electrochemical testing and corresponding XPS analysis also demonstrated that the manganese coordinated by cyanide groups via nitrogen atoms in MnHCF did not get involved in the charge storage process during potential cycles.

Realization of double resonance for a bright frequencytunable source of narrowband entangled photons

In this paper, we report an interesting phenomenon when precisely adjust the tuning crystal for double-resonance of a type-II configured parametric amplifier cavity, which is later verified as a cavity-enhanced effect in optics alignment. The theoretical result indicates that an angle accuracy error within 0.09° is necessary to achieve a high contrast ratio of 100：1 for a cavity with a finesse of about 205, which is crucial but high-demanding to get a high-quality narrowband entanglement source. Meanwhile, we figure out a method to release such a high requirement and get high visibility in a moderate-accuracy alignment.

Preparation of polypyrrole-coated CuFe_2O_4 and their improved electrochemical performance as lithium-ion anodes

CuFe2O4 network,prepared via the electrostatic spray deposition technique,with high reversible capacity and long cycle lifetime for lithium ion battery anode material has been reported.The reversible capacity can be further enhanced by coating high electronic conductive polypyrrole（PPy）.At the current density of 100mA·g-1.Li/CuFe2O4 electrode delivers a reversible capacity of 842.9 mAh·g-1 while the reversible capacity of Li/PPy-coated CuFe2O4 electrode increases up to 1106.7 mAh-g’.A high capacity of 640.7 mAhg＂1 for the Li/PPy-coated CuFe2O4electrode is maintained in contrast of 398.9 mAh·g-1 for CuFe2O4 electrode after 60 cycles,which demonstrates good electrochemical performance of the composite due to the increase of electronic conductivity.The electrochemical impedance spectroscopy（EIS） further reveals that the Li/PPy-coated CuFe2O4 electrode has a lower charge transfer resistance than the Li/CuFe2C〉4 electrode.