Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Co...Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Consequently,it is desired to investigate the mechanisms of the FLP-catalyzed hydrogenation of C=C and C=O and provide insight into the modification of CeO_(2)catalysts for the selective hydrogenation.In this work,the reaction mechanism of the hydrogenation of CH_(2)=CH_(2)and CH_(3)CH=O at the FLP sites constructed on CeO_(2)(110)surface was investigated by density functional theory(DFT),with the classical Lewis acid-base pairs(CLP)site as the reference.The results illustrate that at the CLP site,the dissociated hydride(H^(δ−))forms a stable H−O bond with the surface O atom,while at the FLP site,H^(δ−)is stabilized by Ce,displaying higher activity on the one hand.On the other hand,the electron cloud density of the Ce atom at the FLP site is higher,which can transfer more electrons to the adsorbed C_(C=C)and O_(C=O)atoms,leading to a higher degree of activation for C=C and C=O bonds,as indicated by the Bader charge analysis.Therefore,compared to the CLP site,the FLP site exhibits higher hydrogenation activity for CH_(2)=CH_(2)and CH_(3)CH=O.Furthermore,at the FLP sites,it demonstrates high efficiency in catalyzing the hydrogenation of CH_(2)=CH_(2)with the rate-determining barrier of 1.04 eV,but it shows limited activity for the hydrogenation of CH_(3)CH=O with the rate-determining barrier of 1.94 eV.It means that the selective hydrogenation of C=C can be effectively achieved at the FLP sites concerning selective hydrogenation catalysis.The insights shown in this work help to clarify the reaction mechanism of the hydrogenation of C=C and C=O at FLP site on CeO_(2)(110)and reveal the relationship between the catalytic performance and the nature of the active site,which is of great benefit to development of rational design of heterogeneous FLP catalysts.展开更多
The development of solid frustrated Lewis pairs(FLPs)catalysts with porous structures is a promising strategy for advancing green hydrogenation technologies and has garnered significant attention.Leveraging the divers...The development of solid frustrated Lewis pairs(FLPs)catalysts with porous structures is a promising strategy for advancing green hydrogenation technologies and has garnered significant attention.Leveraging the diverse oxidation states and structural tunability of cerium-based metal-organic frameworks(Ce-MOFs),this study employed a competitive coordination strategy utilizing a single carboxylate functional group ligand to construct a series of MOF-808-X(X=-NH_(2),-OH,-Br,and-NO_(2))featuring rich solid-state FLPs for hydrogenation of unsaturated olefins.The-X functional group serves as a microenvironment,enhancing hydrogenation activity by modulating the electronic properties and acid-base characteristics of the FLP sites.The unique redox properties of elemental cerium facilitate the exposure of unsaturated Ce sites(Ce-CUS,Lewis acid(LA))and adjacent Ce-OH(Lewis base(LB))sites within the MOFs,generating abundant solid-state FLP(Ce-CUS/Ce-OH)sites.Experimental results demonstrate that Ce-CUS and Ce-OH interact with theσandσ^(*)orbitals of H-H,and this"push-pull"synergy promotes heterolytic cleavage of the H-H bond.The lone pair electrons of the electron-donating functional group are transmitted through the molecular backbone to the LB site,thereby increasing its strength and reducing the activation energy required for H_(2)heterolytic cleavage.Notably,at 100℃and 2 MPa H_(2),MOF-808-NH_(2)achieves complete conversion of styrene and dicyclopentadiene,significantly outperforming MOF-808.Based on in-situ analysis and density functional theory calculations,a plausible reaction mechanism is proposed.This research enriches the theoretical framework for unsaturated olefin hydrogenation catalysts and contributes to the development of efficient catalytic systems.展开更多
Long-cycling dendrite-free solid-state lithium metal batteries (LMBs) require fast and uniform lithium-ion (Liþ)transport of solid-state electrolytes (SSEs). However, the SSEs still face the problems of low ionic...Long-cycling dendrite-free solid-state lithium metal batteries (LMBs) require fast and uniform lithium-ion (Liþ)transport of solid-state electrolytes (SSEs). However, the SSEs still face the problems of low ionic conductivity, lowLiþ transference number, and unstable interface with lithium metal. In this work, a novel strategy of frustratedLewis pairs (FLPs) modulating solid polymer electrolytes (SPEs) has been firstly proposed that enables durable Lireversible cycling. The tunable strength of Lewis acid and base dual-active sites of nickel borate FLPs can syn-ergisticallypromote both the dissociation of lithium salts and the transfer of Liþ. As a consequence, the FLPsmodulated SPEs (SPE-NiBO-150) exhibit high ionic conductivity of 4.92×10^(-4)S cm^(-1), high Liþ transferencenumber of 0.74, and superior interface compatibility with both lithium anode and LiFePO4 cathode at room-temperature.The Li//SPE-NiBO-150//Li symmetric cell demonstrates ultralong cycle stability (over 10,000 h(417 days) at both current density of 0.2 and 0.5 mA cm〓〓2), and the assembled solid-state LiFePO4//SPE-NiBO-150//Libattery also shows excellent performance (86% capacity retention for 300 cycles at 0.5C). The presentwork supplies a new insight into designing high-performance SPEs for solid-state LMB applications.展开更多
Spatial confinement of block copolymers can induce frustrations,which can further be utilized to regulate self-assembled structures,thus providing an efficient route for fabricating novel structures.We studied the sel...Spatial confinement of block copolymers can induce frustrations,which can further be utilized to regulate self-assembled structures,thus providing an efficient route for fabricating novel structures.We studied the self-assembly of AB di-block copolymers(di-BCPs)confined in Janus spherical nanocavities using simulations,and explained the structure formation mechanisms.In the case of a strongly selective cavity wall,all the lamella-forming,gyroid-forming,and cylinder-forming di-BCPs can form interfacial frustration-induced Janus concentric perforated lamellar nanoparticles,whose outermost is a Janus spherical shell and the internal is a sphere with concentric perforated lamellar structure.In particular,Janus concentric perforated lamellar nanoparticles with holes distributed only near the equatorial plane were obtained in both lamella-forming and gyroid-forming di-BCPs,directly reflecting the effect of interfacial frustration.The minority-block domain of the cylider-forming di-BCPs may form hemispherical perforated lamellar structures with holes distributed in parallel layers with a specific orientation.For symmetric di-BCPs,both the A and B domains in each nanoparticle are continuous,interchangeable,and have rotational symmetry.While for gyroid-forming and cylinder-forming di-BCPs,only the majority-block domains are continuous in each nanoparticle,and holes in the minority-block domains usually have rotational symmetry.In the case of a weakly selective cavity wall,the inhomogeneity of the cavity wall results in structures having a specific orientation(such as flower-like and branched structures in gyroid-forming and cylinder-forming di-BCPs)and a perforated wetting layer with uniformly distributed holes.The novel nanoparticles obtained may have potential applications in nanotechnology as functional nanostructures or nanoparticles.展开更多
Chiral active matter exhibits a variety of collective behaviors,including phase separation,which is governed by the rule of“like chiralities attract,while opposite chiralities repel”.In this work,we investigate the ...Chiral active matter exhibits a variety of collective behaviors,including phase separation,which is governed by the rule of“like chiralities attract,while opposite chiralities repel”.In this work,we investigate the chiral demixing strategy of double-chiral partial mixture with inter-chiral frustration.We find that the inter-chiral frustration can significantly enhance the chiral demixing of active particles with different chiralities,both during the transient and in the steady state,not only accelerating the progress,but also improving the degree of phase separation.This phenomenon is reminiscent of the phase separation of binary mixtures in condensed matter physics,where the inter-chiral frustration can play a crucial role in the formation of the phase-separated states.We construct the phase diagram of the system and discuss the critical frustration for the enhancement of chiral demixing.Our work presents the first systematic investigation of inter-chiral frustration in self-propelled chiral active matter,filling a critical gap in the field.展开更多
One-step direct production of methanol from methane and water(PMMW)under mild conditions is challenging in heterogeneous catalysis owing to the absence of highly effective catalysts.Herein,we designed a series of“Sin...One-step direct production of methanol from methane and water(PMMW)under mild conditions is challenging in heterogeneous catalysis owing to the absence of highly effective catalysts.Herein,we designed a series of“Single-Atom”-“Frustrated Lewis Pair”(SA-FLP)dual active sites for the direct PMMW via density functional theory(DFT)calculations combined with a machine learning(ML)approach.The results indicate that the nine designed SA-FLP catalysts are capable of efficiently activate CH4 and H_(2)O and facilitate the coupling of OH^(*)and CH_(3)^(*)into methanol.The DFT-based microkinetic simulation(MKM)results indicate that CH_(3)OH production on Co1-FLP and Pt1-FLP catalysts can reach the turnover frequencies(TOFs)of 1.01×10^(−3)s^(-1)and 8.80×10^(−4)s^(-1),respectively,which exceed the experimentally reported values by three orders of magnitude.ML results unveil that the gradient boosted regression model with 13 simple features could give satisfactory predictions for the TOFs of CH_(3)OH production with RMSE and R^(2)of 0.009 s^(-1)and 1.00,respectively.The ML-predicted MKM results indicate that four catalysts including V_(1-),Fe_(1-),Ti_(1-),and Mn_(1)-FLP exhibit higher TOFs of CH_(3)OH production than the value that the most relevant experiments reported,indicating that the four catalysts are also promising catalysts for the PMMW.This study not only develops a simple and efficient approach for design and screening SA-FLP catalysts but also provides mechanistic insights into the direct PMMW.展开更多
We extend a semiclassical numerical method, bosonic auxiliary-field Monte Carlo, to quantum spin systems. This method breaks the lattice into clusters, solves each cluster precisely and couples them with classical aux...We extend a semiclassical numerical method, bosonic auxiliary-field Monte Carlo, to quantum spin systems. This method breaks the lattice into clusters, solves each cluster precisely and couples them with classical auxiliary fields through classical Monte Carlo simulation. We test the method with antiferromagnetic spin models in one-dimensional chains, square lattices and triangular lattices, and obtain reasonable results at finite temperatures. This algorithm builds a bridge between classical Monte Carlo method and quantum methods. The algorithm can be improved with either progress in classical Monte Carlo sampling or the development of quantum solvers, and can also be further applied to systems with different lattices or interactions.展开更多
Frustrated lanthanide oxides with dense magnetic lattice and suppressed ordering temperature have potential applications in cryogenic magnetic refrigeration.Herein,the crystal structure,magnetic properties,magnetic ph...Frustrated lanthanide oxides with dense magnetic lattice and suppressed ordering temperature have potential applications in cryogenic magnetic refrigeration.Herein,the crystal structure,magnetic properties,magnetic phase transition(MPT)together with magnetocaloric effect(MCE)of LnOF(Ln=Gd,Dy,Ho,and Er)compounds were investigated.Crystallographic study shows that these compounds crystallize in the centrosymmetric space group R3m with an ideal triangular lattice.No long-range magnetic ordering is observed above 2 K for LnOF(Ln=Gd,Ho,and Er).However,DyOF compound undergoes an MPT from paramagnetic(PM)to antiferromagnetic(AFM)at the Neel temperature(TN≈4 K).Considerable reversible MCE is observed in these triangular-lattice compounds.Under the magnetic field change(μ0ΔH)of 0-2 T,the maximum values of magnetic entropy change(-ΔSMmax)of them are 6.1,9.4,12.7,and 14.1 J/(kg·K),respectively.Interestingly,the value of ErOF with Ising-like spin is 2.3 times that of GdOF,which provides an approach for exploring magnetic refrigerants with excellent low-field cryogenic magnetocaloric effect.展开更多
Catalytic reduction of 4-nitrophenol(4-NP)pollutant to the high-value 4-aminophenol(4-AP)with a clean hydrogen donor holds significant importance yet great challenges owing to the difficult activation of nitro and H s...Catalytic reduction of 4-nitrophenol(4-NP)pollutant to the high-value 4-aminophenol(4-AP)with a clean hydrogen donor holds significant importance yet great challenges owing to the difficult activation of nitro and H species.In this work,Ag tailoring Frustrated Lewis pairs(FLPs)of CeO_(2)(Ag/CeO_(2))were successfully fabricated for electrochemical reduction reaction of 4-NP(4-NP ERR).As a result,the bond of Ag with O atom changed the state of the Ce-O bond and electron density,where the tailored FLPs were the key factor for enhancing absorption and activation.The reaction rate of Ag/CeO_(2)reached up to 4.70 mmol·min^(-1)(Faraday efficiency:99.5%),which was about four times of CeO_(2).Additionally,this study delved into the proton-coupled electron processes to further understand the mechanism of 4-NP ERR.Therefore,in this study,we have endeavored to investigate the role of tailored FLPs sites and utilize this structure-function relationship to achieve environmentalfriendly chemical synthesis.展开更多
The construction of frustrated Lewis acid-base pairs(FLPs)in porous systems is very important for the field of industrial hydrogenation catalysis,but there is still a great challenge.Based on the Ce^(3+)/Ce^(4+)redox ...The construction of frustrated Lewis acid-base pairs(FLPs)in porous systems is very important for the field of industrial hydrogenation catalysis,but there is still a great challenge.Based on the Ce^(3+)/Ce^(4+)redox pairs and abundant defects in porous Ce-based metal-organic frameworks(Ce-MOFs),FLP sites consisting of ligand-defective Ce sites(Lewis acid,LA)and neighboring terminal O sites(Lewis base,LB)were constructed in situ by a simple vacuum thermal activation method in lamellar Ce-UiO-66-F.Defects/oxygen vacancies in the Ce-MOFs structure result in the difference in the electron cloud density between Ce and O,which is suitable for H-H hetero-cleavage and H-transfer in the dicyclopentadiene(DCPD)hydrogenation process.Particularly,Ce-UiO-66-F-200 achieved 96.9%conversion of DCPD and 97.8%selectivity of 8,9-dihydrodicyclopentadiene(8,9-DHDCPD)at 100℃ under 2MPa H2 for 10 h,which is 9.4 times higher than 10.2%conversion of DCPD over the unactivated Ce-UiO-66-F.This research promotes the understanding of solid MOFs-based porous FLPs for H_(2) activation,and encourages the in-depth investigation of surface solid FLPs to the whole material FLPs.展开更多
Ring polymers are ubiquitous in various fields including biomaterials,drug release and gene therapy.All of these applications involve the dynamics and diffusion process of ring polymers in a confined environment.By us...Ring polymers are ubiquitous in various fields including biomaterials,drug release and gene therapy.All of these applications involve the dynamics and diffusion process of ring polymers in a confined environment.By using dynamic light scattering(DLS),we discovered a dynamical transition for charged ring polymers with increasing ring concentration in the gel matrix from a diffusive state to a non-diffusive topological frustrated state with a more compact conformation.When the ring polymer size is smaller than the mesh size of the gel matrix,the rings are diffusive at low concentration of 5 g/L.The ring diffusion coefficient in the gel matrix is an order of magnitude smaller than that of rings in solution,obeying the Ogston's model.At high ring concentration of 40 g/L,the collective dynamical behavior of the charged rings exhibits a topologically frustrated non-diffusive state,which may originate from the inter-ring threading with the external confinement from the gel matrix.Based on our previous theoretical work,we also conjectured that in such a non-diffusive state,the ring polymers might adopt a more compact conformation with the overall size exponentν=1/3.展开更多
The alkaline hydrogen evolution reaction(HER)is a crucial process for sustainable hydrogen production,yet it requires efficient and stable electrocatalysts to overcome the high activation energy barrier.The article di...The alkaline hydrogen evolution reaction(HER)is a crucial process for sustainable hydrogen production,yet it requires efficient and stable electrocatalysts to overcome the high activation energy barrier.The article discusses a novel strategy for enhancing the performance of Ni-Fe layered double hydroxide(Ni-Fe LDH)in the alkaline HER by modifying it with a frustrated Lewis acid-base pair(FLP)constructed through vacancy engineering.The study found that the modified Ni-Fe LDH exhibited improved alkaline HER performance.Density functional theory(DFT)calculations demonstrate that the introduction of FLP can activate water and protons more efficiently than monometallic sites,thus reducing the alkaline HER energy barrier and overpotential.In HER under alkaline conditions,the Volmer step involves an additional hydrolysis dissociation compared to acidic conditions,which is one of the factors contributing to the slow reaction kinetics.This paper demonstrates that FLPs can alter the rate-determining step in alkaline HER from the Volmer step to a step with a lower energy barrier,more suitable for hydrogen desorption.The work provides new insights into the role of FLPs in regulating the mechanism and kinetics of HER and opens a new direction for the design and optimization of LDH-based and other electrocatalysts.展开更多
Large superconducting Fe Se crystals of（001） orientation have been prepared via a hydrothermal ion release/introduction route for the first time. The hydrothermally derived Fe Se crystals are up to 10 mm×5 mm&#...Large superconducting Fe Se crystals of（001） orientation have been prepared via a hydrothermal ion release/introduction route for the first time. The hydrothermally derived Fe Se crystals are up to 10 mm×5 mm×0.3 mm in dimension. The pure tetragonal FeSe phase has been confirmed by x-ray diffraction（XRD） and the composition determined by both inductively coupled plasma atomic emission spectroscopy（ICP-AES） and energy dispersive x-ray spectroscopy（EDX）. The superconducting transition of the Fe Se samples has been characterized by magnetic and transport measurements. The zero-temperature upper critical field H（c2） is calculated to be 13.2–16.7 T from a two-band model. The normal-state cooperative paramagnetism is found to be predominated by strong spin frustrations below the characteristic temperature T（sn）, where the Ising spin nematicity has been discerned in the FeSe superconductor crystals as reported elsewhere.展开更多
frustrated Lewis pair(FLP)是一个最近出现的新名词,指分子内或混合体系中同时具有路易斯酸和路易斯碱两个位点,由于空间位阻较大而使得这两个位点不能结合形成路易斯酸碱加合物,从而具有独特的反应活性。建议译为"受阻路易斯酸碱...frustrated Lewis pair(FLP)是一个最近出现的新名词,指分子内或混合体系中同时具有路易斯酸和路易斯碱两个位点,由于空间位阻较大而使得这两个位点不能结合形成路易斯酸碱加合物,从而具有独特的反应活性。建议译为"受阻路易斯酸碱对"。展开更多
Objective:The purpose of this qualitative study was to describe the experiences of pain acceptance in Chinese cancer patients with chronic pain.Methods:Twelve hospitalized cancer patients with chronic pain participate...Objective:The purpose of this qualitative study was to describe the experiences of pain acceptance in Chinese cancer patients with chronic pain.Methods:Twelve hospitalized cancer patients with chronic pain participated in this qualitative descriptive study from August to November 2017.In-person semi-structured interviews were conducted,recorded,transcribed,and analyzed using Colaizzi's seven-step method.Results:The following four main themes and 15 subthemes emerged.Theme 1(adaptation):pain is overwhelming and pain relief is a top priority,avoidance of pain-inducing factors,and resignation;theme 2(emotional reactions to pain):feeling misunderstood,hopelessness,frustration,irritability,and concern for loved ones;theme 3(functional limitations):daily life activities,social communication,and work;theme 4(coping strategies):pharmacological therapies,behavioral strategies,social support strategies,and spiritual strategies.Conclusions:This study provides a description of cancer patients'experiences related to the need for pain acceptance.These findings provide insight into the essential role of pain acceptance and underline the need to apply acceptance-based cognitive behavioral interventions as adjunctive non-pharmacological alternatives for chronic cancer pain.展开更多
Over the past decade,multistable mechanical metamaterials have been widely investigated because of their novel shape reconfigurability and programmable energy landscape.The ability to reversibly reshape among diverse ...Over the past decade,multistable mechanical metamaterials have been widely investigated because of their novel shape reconfigurability and programmable energy landscape.The ability to reversibly reshape among diverse stable states with different energy levels represents the most important feature of the multistable mechanical metamaterials.We summarize main design strategies of multistable mechanical metamaterials,including those based on self-assembly scheme,snap-through instability,structured mechanism and geometrical frustration,with a focus on the number and controllability of accessible stable states.Then we concentrate on unusual mechanical properties of these multistable mechanical metamaterials,and present their applications in a wide range of areas,including tunable electromagnetic devices,actuators,robotics,and mechanical logic gates.Finally,we discuss remaining challenges and open opportunities of designs and applications of multistable mechanical metamaterials.展开更多
The sciatic functional index（SFI） is a popular parameter for peripheral nerve evaluation that relies on footprints obtained with ink and paper. Drawbacks include smearing artefacts and a lack of dynamic information ...The sciatic functional index（SFI） is a popular parameter for peripheral nerve evaluation that relies on footprints obtained with ink and paper. Drawbacks include smearing artefacts and a lack of dynamic information during measurement. Modern applications use digitized systems that can deliver results with less analytical effort and fewer mice. However, the systems are expensive（€40,000）. This study aimed to evaluate the applicability and precision of a self-made, low-cost infrared system for evaluating SFI in mice. Mice were subjected to unilateral sciatic nerve crush injury（crush group; n = 7） and sham operation（sham group; n = 4）. They were evaluated on the day before surgery, the 2nd, 4th and 6th days after injury, and then every day up to the 23rd day after injury. We compared two SFI evaluation methods, i.e., conventional inkand-paper SFI（C-SFI） and our infrared system（I-SFI）. Our apparatus visualized footprints with totally internally reflected infrared light（950 nm） and a camera that can only detect this wavelength. Additionally we performed an analysis with the ladder beam walking test（LBWT） as a reference test. I-SFI assessment reduced the standard deviation by about 33 percent, from 11.6 to 7.8, and cut the variance around the baseline to 21 percent. The system thus requires fewer measurement repetitions and fewer animals, and cuts the cost of keeping the animals. The apparatus cost €321 to build. Our results show that the process of obtaining the SFI can be made more precise via digitization with a self-made, low-cost infrared system.展开更多
The magnetic and electronic properties of the geometrically frustrated triangular antiferromagnet CuCrO2 are investigated by first principles through density functional theory calculations within the generalized gradi...The magnetic and electronic properties of the geometrically frustrated triangular antiferromagnet CuCrO2 are investigated by first principles through density functional theory calculations within the generalized gradient approxi- mations （GGA）＋U scheme. The spin exchange interactions up to the third nearest neighbours in the ab plane as well as the coupling between adjacent layers are calculated to examine the magnetism and spin frustration. It is found that CuCrO2 has a natural two-dimensional characteristic of the magnetic interaction. Using Monte Carlo simulation, we obtain the Neel temperature to be 29.9 K, which accords well with the experimental value of 24 K. Based on non- collinear magnetic structure calculations, we verify that the incommensurate spiral-spin structure with （110） spiral plane is believable for the magnetic ground state, which is consistent with the experimental observations. Due to intra-layer geometric spin frustration, parallel helical-spin chains arise along the a, b, or a＋ b directions, each with a screw-rotation angle of about I20°. Our calculations of the density of states show that the spin frustration plays an important role in the change of d-p hybridization, while the spin-orbit coupling has a very limited influence on the electronic structure.展开更多
基金supported by the National Natural Science Foundation of China(22302115,22072079)the Fundamental Research Program of Shanxi Province(202303021221056).
文摘Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Consequently,it is desired to investigate the mechanisms of the FLP-catalyzed hydrogenation of C=C and C=O and provide insight into the modification of CeO_(2)catalysts for the selective hydrogenation.In this work,the reaction mechanism of the hydrogenation of CH_(2)=CH_(2)and CH_(3)CH=O at the FLP sites constructed on CeO_(2)(110)surface was investigated by density functional theory(DFT),with the classical Lewis acid-base pairs(CLP)site as the reference.The results illustrate that at the CLP site,the dissociated hydride(H^(δ−))forms a stable H−O bond with the surface O atom,while at the FLP site,H^(δ−)is stabilized by Ce,displaying higher activity on the one hand.On the other hand,the electron cloud density of the Ce atom at the FLP site is higher,which can transfer more electrons to the adsorbed C_(C=C)and O_(C=O)atoms,leading to a higher degree of activation for C=C and C=O bonds,as indicated by the Bader charge analysis.Therefore,compared to the CLP site,the FLP site exhibits higher hydrogenation activity for CH_(2)=CH_(2)and CH_(3)CH=O.Furthermore,at the FLP sites,it demonstrates high efficiency in catalyzing the hydrogenation of CH_(2)=CH_(2)with the rate-determining barrier of 1.04 eV,but it shows limited activity for the hydrogenation of CH_(3)CH=O with the rate-determining barrier of 1.94 eV.It means that the selective hydrogenation of C=C can be effectively achieved at the FLP sites concerning selective hydrogenation catalysis.The insights shown in this work help to clarify the reaction mechanism of the hydrogenation of C=C and C=O at FLP site on CeO_(2)(110)and reveal the relationship between the catalytic performance and the nature of the active site,which is of great benefit to development of rational design of heterogeneous FLP catalysts.
文摘The development of solid frustrated Lewis pairs(FLPs)catalysts with porous structures is a promising strategy for advancing green hydrogenation technologies and has garnered significant attention.Leveraging the diverse oxidation states and structural tunability of cerium-based metal-organic frameworks(Ce-MOFs),this study employed a competitive coordination strategy utilizing a single carboxylate functional group ligand to construct a series of MOF-808-X(X=-NH_(2),-OH,-Br,and-NO_(2))featuring rich solid-state FLPs for hydrogenation of unsaturated olefins.The-X functional group serves as a microenvironment,enhancing hydrogenation activity by modulating the electronic properties and acid-base characteristics of the FLP sites.The unique redox properties of elemental cerium facilitate the exposure of unsaturated Ce sites(Ce-CUS,Lewis acid(LA))and adjacent Ce-OH(Lewis base(LB))sites within the MOFs,generating abundant solid-state FLP(Ce-CUS/Ce-OH)sites.Experimental results demonstrate that Ce-CUS and Ce-OH interact with theσandσ^(*)orbitals of H-H,and this"push-pull"synergy promotes heterolytic cleavage of the H-H bond.The lone pair electrons of the electron-donating functional group are transmitted through the molecular backbone to the LB site,thereby increasing its strength and reducing the activation energy required for H_(2)heterolytic cleavage.Notably,at 100℃and 2 MPa H_(2),MOF-808-NH_(2)achieves complete conversion of styrene and dicyclopentadiene,significantly outperforming MOF-808.Based on in-situ analysis and density functional theory calculations,a plausible reaction mechanism is proposed.This research enriches the theoretical framework for unsaturated olefin hydrogenation catalysts and contributes to the development of efficient catalytic systems.
基金supported by the National Natural Science Foundation of China(52162036,52174284 and 22378342)the Key Project of Nature Science Foundation of Xinjiang Province(2021D01D08)the Key Research and Development Program of Hunan Province(2024JK2094).
文摘Long-cycling dendrite-free solid-state lithium metal batteries (LMBs) require fast and uniform lithium-ion (Liþ)transport of solid-state electrolytes (SSEs). However, the SSEs still face the problems of low ionic conductivity, lowLiþ transference number, and unstable interface with lithium metal. In this work, a novel strategy of frustratedLewis pairs (FLPs) modulating solid polymer electrolytes (SPEs) has been firstly proposed that enables durable Lireversible cycling. The tunable strength of Lewis acid and base dual-active sites of nickel borate FLPs can syn-ergisticallypromote both the dissociation of lithium salts and the transfer of Liþ. As a consequence, the FLPsmodulated SPEs (SPE-NiBO-150) exhibit high ionic conductivity of 4.92×10^(-4)S cm^(-1), high Liþ transferencenumber of 0.74, and superior interface compatibility with both lithium anode and LiFePO4 cathode at room-temperature.The Li//SPE-NiBO-150//Li symmetric cell demonstrates ultralong cycle stability (over 10,000 h(417 days) at both current density of 0.2 and 0.5 mA cm〓〓2), and the assembled solid-state LiFePO4//SPE-NiBO-150//Libattery also shows excellent performance (86% capacity retention for 300 cycles at 0.5C). The presentwork supplies a new insight into designing high-performance SPEs for solid-state LMB applications.
基金supported by the National Natural Science Foundation of China(NSFC)(Nos.22173051,21829301,21774066)College Discipline Innovation and Intelligence Introduction Program(111 Project(B16027)+1 种基金the International Cooperation Base(2016D01025)Tianjin International Joint Research and Development Center。
文摘Spatial confinement of block copolymers can induce frustrations,which can further be utilized to regulate self-assembled structures,thus providing an efficient route for fabricating novel structures.We studied the self-assembly of AB di-block copolymers(di-BCPs)confined in Janus spherical nanocavities using simulations,and explained the structure formation mechanisms.In the case of a strongly selective cavity wall,all the lamella-forming,gyroid-forming,and cylinder-forming di-BCPs can form interfacial frustration-induced Janus concentric perforated lamellar nanoparticles,whose outermost is a Janus spherical shell and the internal is a sphere with concentric perforated lamellar structure.In particular,Janus concentric perforated lamellar nanoparticles with holes distributed only near the equatorial plane were obtained in both lamella-forming and gyroid-forming di-BCPs,directly reflecting the effect of interfacial frustration.The minority-block domain of the cylider-forming di-BCPs may form hemispherical perforated lamellar structures with holes distributed in parallel layers with a specific orientation.For symmetric di-BCPs,both the A and B domains in each nanoparticle are continuous,interchangeable,and have rotational symmetry.While for gyroid-forming and cylinder-forming di-BCPs,only the majority-block domains are continuous in each nanoparticle,and holes in the minority-block domains usually have rotational symmetry.In the case of a weakly selective cavity wall,the inhomogeneity of the cavity wall results in structures having a specific orientation(such as flower-like and branched structures in gyroid-forming and cylinder-forming di-BCPs)and a perforated wetting layer with uniformly distributed holes.The novel nanoparticles obtained may have potential applications in nanotechnology as functional nanostructures or nanoparticles.
基金supported by the National Natural Science Foun-dation of China(Grant Nos.12375031 and 11875135)China National University Student Innovation and Entrepreneurship(Grant No.202410385040)Fujian University Alliance of Physics Discipline Training Program of Innovation for Under-graduates Development Program,China.
文摘Chiral active matter exhibits a variety of collective behaviors,including phase separation,which is governed by the rule of“like chiralities attract,while opposite chiralities repel”.In this work,we investigate the chiral demixing strategy of double-chiral partial mixture with inter-chiral frustration.We find that the inter-chiral frustration can significantly enhance the chiral demixing of active particles with different chiralities,both during the transient and in the steady state,not only accelerating the progress,but also improving the degree of phase separation.This phenomenon is reminiscent of the phase separation of binary mixtures in condensed matter physics,where the inter-chiral frustration can play a crucial role in the formation of the phase-separated states.We construct the phase diagram of the system and discuss the critical frustration for the enhancement of chiral demixing.Our work presents the first systematic investigation of inter-chiral frustration in self-propelled chiral active matter,filling a critical gap in the field.
文摘One-step direct production of methanol from methane and water(PMMW)under mild conditions is challenging in heterogeneous catalysis owing to the absence of highly effective catalysts.Herein,we designed a series of“Single-Atom”-“Frustrated Lewis Pair”(SA-FLP)dual active sites for the direct PMMW via density functional theory(DFT)calculations combined with a machine learning(ML)approach.The results indicate that the nine designed SA-FLP catalysts are capable of efficiently activate CH4 and H_(2)O and facilitate the coupling of OH^(*)and CH_(3)^(*)into methanol.The DFT-based microkinetic simulation(MKM)results indicate that CH_(3)OH production on Co1-FLP and Pt1-FLP catalysts can reach the turnover frequencies(TOFs)of 1.01×10^(−3)s^(-1)and 8.80×10^(−4)s^(-1),respectively,which exceed the experimentally reported values by three orders of magnitude.ML results unveil that the gradient boosted regression model with 13 simple features could give satisfactory predictions for the TOFs of CH_(3)OH production with RMSE and R^(2)of 0.009 s^(-1)and 1.00,respectively.The ML-predicted MKM results indicate that four catalysts including V_(1-),Fe_(1-),Ti_(1-),and Mn_(1)-FLP exhibit higher TOFs of CH_(3)OH production than the value that the most relevant experiments reported,indicating that the four catalysts are also promising catalysts for the PMMW.This study not only develops a simple and efficient approach for design and screening SA-FLP catalysts but also provides mechanistic insights into the direct PMMW.
基金supports by the National Key Research and Development Program of China (Grant No.2024YFA1409200)the National Natural Science Foundation of China (Grant Nos.12222412 and 12047503)+1 种基金CAS Project for Young Scientists in Basic Research (Grant No.YSBR-057)supports by the National Natural Science Foundation of China (Grant No.12374144)。
文摘We extend a semiclassical numerical method, bosonic auxiliary-field Monte Carlo, to quantum spin systems. This method breaks the lattice into clusters, solves each cluster precisely and couples them with classical auxiliary fields through classical Monte Carlo simulation. We test the method with antiferromagnetic spin models in one-dimensional chains, square lattices and triangular lattices, and obtain reasonable results at finite temperatures. This algorithm builds a bridge between classical Monte Carlo method and quantum methods. The algorithm can be improved with either progress in classical Monte Carlo sampling or the development of quantum solvers, and can also be further applied to systems with different lattices or interactions.
基金Project supported by the National Key Research and Development Program of China(2022YFB3505101)the National Science Foundation for Excellent Young Scholars(52222107)+2 种基金the National Science Foundation for Distinguished Young Scholars(51925605)the National Natural Science Foundation of China(52171195)the Projects of Ganjiang Innovation Academy,Chinese Academy of Sciences(E055B002)。
文摘Frustrated lanthanide oxides with dense magnetic lattice and suppressed ordering temperature have potential applications in cryogenic magnetic refrigeration.Herein,the crystal structure,magnetic properties,magnetic phase transition(MPT)together with magnetocaloric effect(MCE)of LnOF(Ln=Gd,Dy,Ho,and Er)compounds were investigated.Crystallographic study shows that these compounds crystallize in the centrosymmetric space group R3m with an ideal triangular lattice.No long-range magnetic ordering is observed above 2 K for LnOF(Ln=Gd,Ho,and Er).However,DyOF compound undergoes an MPT from paramagnetic(PM)to antiferromagnetic(AFM)at the Neel temperature(TN≈4 K).Considerable reversible MCE is observed in these triangular-lattice compounds.Under the magnetic field change(μ0ΔH)of 0-2 T,the maximum values of magnetic entropy change(-ΔSMmax)of them are 6.1,9.4,12.7,and 14.1 J/(kg·K),respectively.Interestingly,the value of ErOF with Ising-like spin is 2.3 times that of GdOF,which provides an approach for exploring magnetic refrigerants with excellent low-field cryogenic magnetocaloric effect.
基金supported by National Natural Science Foundation of China(22075112)Opening Foundation of State Key Laboratory of Rare Earth Resource Utilization(RERU2023010)+1 种基金Opening Foundation of Key Laboratory of Functional Inorganic Material Chemistry(Heilongjiang University)Ministry of Education,China,Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX24_4006).
文摘Catalytic reduction of 4-nitrophenol(4-NP)pollutant to the high-value 4-aminophenol(4-AP)with a clean hydrogen donor holds significant importance yet great challenges owing to the difficult activation of nitro and H species.In this work,Ag tailoring Frustrated Lewis pairs(FLPs)of CeO_(2)(Ag/CeO_(2))were successfully fabricated for electrochemical reduction reaction of 4-NP(4-NP ERR).As a result,the bond of Ag with O atom changed the state of the Ce-O bond and electron density,where the tailored FLPs were the key factor for enhancing absorption and activation.The reaction rate of Ag/CeO_(2)reached up to 4.70 mmol·min^(-1)(Faraday efficiency:99.5%),which was about four times of CeO_(2).Additionally,this study delved into the proton-coupled electron processes to further understand the mechanism of 4-NP ERR.Therefore,in this study,we have endeavored to investigate the role of tailored FLPs sites and utilize this structure-function relationship to achieve environmentalfriendly chemical synthesis.
基金supported by the National Key Research and Development Program of China(No.2021YFB3500700)the National Natural Science Foundation of China(No.51972024)+1 种基金Natural Science Foundation of Guangdong Province(No.2022A1515010185)Fundamental Research Funds for the Central Universities(No.FRFEYIT-23-07).
文摘The construction of frustrated Lewis acid-base pairs(FLPs)in porous systems is very important for the field of industrial hydrogenation catalysis,but there is still a great challenge.Based on the Ce^(3+)/Ce^(4+)redox pairs and abundant defects in porous Ce-based metal-organic frameworks(Ce-MOFs),FLP sites consisting of ligand-defective Ce sites(Lewis acid,LA)and neighboring terminal O sites(Lewis base,LB)were constructed in situ by a simple vacuum thermal activation method in lamellar Ce-UiO-66-F.Defects/oxygen vacancies in the Ce-MOFs structure result in the difference in the electron cloud density between Ce and O,which is suitable for H-H hetero-cleavage and H-transfer in the dicyclopentadiene(DCPD)hydrogenation process.Particularly,Ce-UiO-66-F-200 achieved 96.9%conversion of DCPD and 97.8%selectivity of 8,9-dihydrodicyclopentadiene(8,9-DHDCPD)at 100℃ under 2MPa H2 for 10 h,which is 9.4 times higher than 10.2%conversion of DCPD over the unactivated Ce-UiO-66-F.This research promotes the understanding of solid MOFs-based porous FLPs for H_(2) activation,and encourages the in-depth investigation of surface solid FLPs to the whole material FLPs.
基金supported by the National Natural Science Foundation of China(No.22273114)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0770101)+1 种基金the National Key R&D Program of China(No.2023YFE0124500),the National Key R&D Program of China(No.2023YFC2411203)International Partnership Program of the Chinese Academy of Sciences(No.027GJHZ2022061FN)。
文摘Ring polymers are ubiquitous in various fields including biomaterials,drug release and gene therapy.All of these applications involve the dynamics and diffusion process of ring polymers in a confined environment.By using dynamic light scattering(DLS),we discovered a dynamical transition for charged ring polymers with increasing ring concentration in the gel matrix from a diffusive state to a non-diffusive topological frustrated state with a more compact conformation.When the ring polymer size is smaller than the mesh size of the gel matrix,the rings are diffusive at low concentration of 5 g/L.The ring diffusion coefficient in the gel matrix is an order of magnitude smaller than that of rings in solution,obeying the Ogston's model.At high ring concentration of 40 g/L,the collective dynamical behavior of the charged rings exhibits a topologically frustrated non-diffusive state,which may originate from the inter-ring threading with the external confinement from the gel matrix.Based on our previous theoretical work,we also conjectured that in such a non-diffusive state,the ring polymers might adopt a more compact conformation with the overall size exponentν=1/3.
基金financially supported by National Natural Science Foundation of China(Nos.52301011,52231008,52142304,52177220,U23A200767,52302236,and 22369005)Hainan Provincial Natural Science Foundation of China(Nos.524QN226 and 524QN222)+2 种基金the Key Research and Development Program of Hainan Province(No.ZDYF2022GXJS006)Starting Research Fund from the Hainan University(No.KYQD(ZR)23026)International Science&Technology Cooperation Program of Hainan Province(No.GHYF2023007).
文摘The alkaline hydrogen evolution reaction(HER)is a crucial process for sustainable hydrogen production,yet it requires efficient and stable electrocatalysts to overcome the high activation energy barrier.The article discusses a novel strategy for enhancing the performance of Ni-Fe layered double hydroxide(Ni-Fe LDH)in the alkaline HER by modifying it with a frustrated Lewis acid-base pair(FLP)constructed through vacancy engineering.The study found that the modified Ni-Fe LDH exhibited improved alkaline HER performance.Density functional theory(DFT)calculations demonstrate that the introduction of FLP can activate water and protons more efficiently than monometallic sites,thus reducing the alkaline HER energy barrier and overpotential.In HER under alkaline conditions,the Volmer step involves an additional hydrolysis dissociation compared to acidic conditions,which is one of the factors contributing to the slow reaction kinetics.This paper demonstrates that FLPs can alter the rate-determining step in alkaline HER from the Volmer step to a step with a lower energy barrier,more suitable for hydrogen desorption.The work provides new insights into the role of FLPs in regulating the mechanism and kinetics of HER and opens a new direction for the design and optimization of LDH-based and other electrocatalysts.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11574370,11274358,and 11190020)the National Basic Research Program of China(Grant No.2013CB921700)the Strategic Priority Research Program(B)of the Chinese Academy of Sciences(Grant No.XDB07020100)
文摘Large superconducting Fe Se crystals of（001） orientation have been prepared via a hydrothermal ion release/introduction route for the first time. The hydrothermally derived Fe Se crystals are up to 10 mm×5 mm×0.3 mm in dimension. The pure tetragonal FeSe phase has been confirmed by x-ray diffraction（XRD） and the composition determined by both inductively coupled plasma atomic emission spectroscopy（ICP-AES） and energy dispersive x-ray spectroscopy（EDX）. The superconducting transition of the Fe Se samples has been characterized by magnetic and transport measurements. The zero-temperature upper critical field H（c2） is calculated to be 13.2–16.7 T from a two-band model. The normal-state cooperative paramagnetism is found to be predominated by strong spin frustrations below the characteristic temperature T（sn）, where the Ising spin nematicity has been discerned in the FeSe superconductor crystals as reported elsewhere.
基金supported by the Hunan Provincial Natural Science Fund,China,grant number 2018JJ6110
文摘Objective:The purpose of this qualitative study was to describe the experiences of pain acceptance in Chinese cancer patients with chronic pain.Methods:Twelve hospitalized cancer patients with chronic pain participated in this qualitative descriptive study from August to November 2017.In-person semi-structured interviews were conducted,recorded,transcribed,and analyzed using Colaizzi's seven-step method.Results:The following four main themes and 15 subthemes emerged.Theme 1(adaptation):pain is overwhelming and pain relief is a top priority,avoidance of pain-inducing factors,and resignation;theme 2(emotional reactions to pain):feeling misunderstood,hopelessness,frustration,irritability,and concern for loved ones;theme 3(functional limitations):daily life activities,social communication,and work;theme 4(coping strategies):pharmacological therapies,behavioral strategies,social support strategies,and spiritual strategies.Conclusions:This study provides a description of cancer patients'experiences related to the need for pain acceptance.These findings provide insight into the essential role of pain acceptance and underline the need to apply acceptance-based cognitive behavioral interventions as adjunctive non-pharmacological alternatives for chronic cancer pain.
基金supported by the National Natural Science Foundation of China(No.11722217)the Tsinghua University,China Initiative Scientific Research Program(No.2019Z08QCX10)the Institute for Guo Qiang,Tsinghua University,China(No.2019GQG1012)。
文摘Over the past decade,multistable mechanical metamaterials have been widely investigated because of their novel shape reconfigurability and programmable energy landscape.The ability to reversibly reshape among diverse stable states with different energy levels represents the most important feature of the multistable mechanical metamaterials.We summarize main design strategies of multistable mechanical metamaterials,including those based on self-assembly scheme,snap-through instability,structured mechanism and geometrical frustration,with a focus on the number and controllability of accessible stable states.Then we concentrate on unusual mechanical properties of these multistable mechanical metamaterials,and present their applications in a wide range of areas,including tunable electromagnetic devices,actuators,robotics,and mechanical logic gates.Finally,we discuss remaining challenges and open opportunities of designs and applications of multistable mechanical metamaterials.
文摘The sciatic functional index（SFI） is a popular parameter for peripheral nerve evaluation that relies on footprints obtained with ink and paper. Drawbacks include smearing artefacts and a lack of dynamic information during measurement. Modern applications use digitized systems that can deliver results with less analytical effort and fewer mice. However, the systems are expensive（€40,000）. This study aimed to evaluate the applicability and precision of a self-made, low-cost infrared system for evaluating SFI in mice. Mice were subjected to unilateral sciatic nerve crush injury（crush group; n = 7） and sham operation（sham group; n = 4）. They were evaluated on the day before surgery, the 2nd, 4th and 6th days after injury, and then every day up to the 23rd day after injury. We compared two SFI evaluation methods, i.e., conventional inkand-paper SFI（C-SFI） and our infrared system（I-SFI）. Our apparatus visualized footprints with totally internally reflected infrared light（950 nm） and a camera that can only detect this wavelength. Additionally we performed an analysis with the ladder beam walking test（LBWT） as a reference test. I-SFI assessment reduced the standard deviation by about 33 percent, from 11.6 to 7.8, and cut the variance around the baseline to 21 percent. The system thus requires fewer measurement repetitions and fewer animals, and cuts the cost of keeping the animals. The apparatus cost €321 to build. Our results show that the process of obtaining the SFI can be made more precise via digitization with a self-made, low-cost infrared system.
基金Project supported by the National Natural Science Foundation of China (Grant No. 10874021)
文摘The magnetic and electronic properties of the geometrically frustrated triangular antiferromagnet CuCrO2 are investigated by first principles through density functional theory calculations within the generalized gradient approxi- mations （GGA）＋U scheme. The spin exchange interactions up to the third nearest neighbours in the ab plane as well as the coupling between adjacent layers are calculated to examine the magnetism and spin frustration. It is found that CuCrO2 has a natural two-dimensional characteristic of the magnetic interaction. Using Monte Carlo simulation, we obtain the Neel temperature to be 29.9 K, which accords well with the experimental value of 24 K. Based on non- collinear magnetic structure calculations, we verify that the incommensurate spiral-spin structure with （110） spiral plane is believable for the magnetic ground state, which is consistent with the experimental observations. Due to intra-layer geometric spin frustration, parallel helical-spin chains arise along the a, b, or a＋ b directions, each with a screw-rotation angle of about I20°. Our calculations of the density of states show that the spin frustration plays an important role in the change of d-p hybridization, while the spin-orbit coupling has a very limited influence on the electronic structure.
