The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycl...The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.展开更多
The electrochemical conversion of nitrate,a widespread water pollutant,into valuable ammonia represents a green and decentralized approach to ammonia synthesis.However,the sluggish multielectronproton coupling path an...The electrochemical conversion of nitrate,a widespread water pollutant,into valuable ammonia represents a green and decentralized approach to ammonia synthesis.However,the sluggish multielectronproton coupling path and the low reactive species(nitrate and proton)concentration at the catalyst interface inhibit the efficiency of ammonia production from nitrate reduction reaction(NitRR).Herein,we introduce a novel iron-based tandem catalyst encapsulated by reduced graphene oxide(denoted as Fe-rGO),with a superior ammonia production rate of 47.815 mg h^(-1)mg_(ca)^(t-1)and a high Faraday efficiency(FE)of 96.51%at an applied potential of-0.5 V.It also delivers a robust stability with FE above90%under a current density of 250 mA cm^(-2)for 50 h.In situ X-ray absorption spectroscopy reveals that the FeO_(x)is dynamically translated to Fe~0 site concurrently with the enhancement of the NH_(3)production rate,suggesting the Fe^(0) site as hydrogenation active center.The asymmetric distribution of surface charges of rGO not only enriches nitrate ions at the catalytic interface and promotes the hydrogenation process in NitRR,but also protects the iron species and ensures their stability during electrolysis.The Zn-NO_(3)^(-)battery demonstrates an impressive FE of 88.6%,highlighting its exceptional potential for practical applications.展开更多
Nickel-rich LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)(NCM)cathodes,pivotal for high-energy-density lithium-ion batteries,face severe challenges from surface residual lithium compounds and hydrofluoric acid(HF)-induced degradation...Nickel-rich LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)(NCM)cathodes,pivotal for high-energy-density lithium-ion batteries,face severe challenges from surface residual lithium compounds and hydrofluoric acid(HF)-induced degradation.These issues accelerate capacity fading,exacerbate interfacial polarization,and compromise safety.To address these issues,we proposed a scalable CeF_(3)/H_(3)BO_(3)hybrid coating strategy for LiNi_(0.82)Co_(0.12)Mn_(0.06)O_(2)cathodes.The CeF_(3)nanoparticles served as a robust physical barrier,effectively scavenging HF,while the LiBO_(2)layer derived from H_(3)BO_(3)eliminated residual Li_(2)CO_(3)through chemical conversion and established rapid Li^(+)transport pathways.Dynamic B-O bond reorganization enabled self-repair of coating defects,synergistically suppressing interfacial polarization and maintaining structural integrity.Electrochemical evaluations demonstrated that the hybridcoated cathode achieves 94%capacity retention after 200 cycles at 1C(2.8-4.3 V),significantly outperforming the pristine NCM(56.3%).Additionally,the modified cathode exhibits enhanced air stability,with suppressed H_(2)O/CO_(2)infiltration,and delivers 80%capacity retention after 1000 cycles in practical pouch cells.This work provides a costeffective and industrially viable solution to simultaneously mitigate HF corrosion,residual lithium accumulation,and cathode-electrolyte interphase instability,paving the way for durable high-energy-density batteries.展开更多
Dispersing metals from nanoparticles to clusters is often achieved using ligand protection methods,which exhibit unique properties such as suppressing structure-sensitive side reactions.However,this method is limited ...Dispersing metals from nanoparticles to clusters is often achieved using ligand protection methods,which exhibit unique properties such as suppressing structure-sensitive side reactions.However,this method is limited by the use of different metal precursor salts corresponding to different ligands.An alternative approach,the ion exchange(IE)method,can overcome this limitation to some extent.Nevertheless,there is still an urgent need to address the stabilization of metals(especially precious metals)by using IE method.Here,we reported a Pt cluster catalyst prepared mainly by anchoring Pt atoms via O located near the framework Zn in zincosilicate zeolites and riveted by zeolite surface rings after reduction(reduced Pt/Zn-3-IE).The catalyst can achieve an initial propane conversion of 26%in a pure propane atmosphere at 550℃and shows little deactivation even after 7.5 d of operation.Moreover,the alteration of catalyst by the introduction of framework Zn was also highlighted and interpreted.展开更多
The prelithiated SiO_(x)anode showcases markedly improved Li-storage capabilities compared to its unlithiated counterparts,yet it faces hurdles such as slurry gassing,electrolyte deterioration,and capacity fade attrib...The prelithiated SiO_(x)anode showcases markedly improved Li-storage capabilities compared to its unlithiated counterparts,yet it faces hurdles such as slurry gassing,electrolyte deterioration,and capacity fade attributed to residual alkali and an unstable electrolyte/anode interface.To tackle these challenges,we propose a strategic utilization of residual alkali by creating an in-situ γ-LiAlO_(2)functional layer on the prelithiated SiO_(x)@C anode material.This is accomplished by incorporating a minor amount of Al_(2)O_(3)into the SiO_(x)@C/LiH precursor mixture before the solid-phase prelithiation process.The resulting modified prelithiated SiO_(x)@C anode with in-situ formed electrolyte-isolatingγ-LiAlO_(2)layer exhibits no discernible slurry gas generation within 7 days and substantially mitigates side reactions with the electrolyte,thereby boosting the initial coulombic efficiency and cycling stability of the SiO_(x)@C anode.In half-cell evaluations,the prelithiated SiO_(x)@C anode demonstrates a high Li-storage capacity of 1323 mAh g^(-1)and an impressive initial coulombic efficiency of 91.09%.When assessed in a 3.2 Ah 18,650 cylindrical battery,the prelithiated SiO_(x)@C anode showcases exceptional cyclability,retaining 81% of its capacity after 1000 cycles,underscoring its potential for practical applications.This study introduces a scalable and cost-effective prelithiation technique that propels the development and practical deployment of Si-based anodes by resolving persistent scientific challenges with the use of inexpensive additives.展开更多
The Li-CO_(2)battery has been highly rated as an intriguing technique for balancing the carbon cycle for years,but it is still significantly challenged by the obstacles such as limited reversibility,sluggish kinetics,...The Li-CO_(2)battery has been highly rated as an intriguing technique for balancing the carbon cycle for years,but it is still significantly challenged by the obstacles such as limited reversibility,sluggish kinetics,and poor energy efficiency.Hence,the design and development of advance catalysts that can enhance the kinetics and reversibility of the CO_(2)electrochemical cycling reactions are considered the imperative tasks.Transition metal-based catalysts are widely considered appealing owing to their unfilled dorbitals,rich and adjustable valences,as well as processibility.In this review,the working mechanism and the key issues of the CO_(2)electrochemical cycling reaction are discussed first.Then the strategies for composition and structure design of different type of transition metal-based catalysts are highlighted,including their benefits,limitations,and the ways to implement these strategies.Finally,based on the pioneering research,the perspectives on the challenges and key points for the future development of cathode catalyst are proposed.展开更多
Covalent crosslinking points within thermosets generally result in excellent mechanical properties and solvent resistance yet lead to limited degradability and recyclability.Those thermosets become degradable or recyc...Covalent crosslinking points within thermosets generally result in excellent mechanical properties and solvent resistance yet lead to limited degradability and recyclability.Those thermosets become degradable or recyclable if crosslinking points are cleavable or reversible.Following this principle,we report a kind of polyurea-urethane thermoset with borate ester as its crosslinking point to enable a controllable decrosslinking in response to acetate acid.Such a thermoset presents remarkable mechanical properties as well as outstanding solvent resistance capability,due to the high crosslinking density and intermolecular hydrogen bonding.Furthermore,the de-crosslinked product can be reporcessed to generate a brand new thermoplastic material.展开更多
The presence of defects and detrimental reactions at NiO_(x)/perovskite interface extremely limit the efficiency performance and long-term stability of the perovskite solar cells(PSCs) based on NiO_(x).Herein,an amphi...The presence of defects and detrimental reactions at NiO_(x)/perovskite interface extremely limit the efficiency performance and long-term stability of the perovskite solar cells(PSCs) based on NiO_(x).Herein,an amphipathic molecule Triton X100(Triton) is modified on the NiO_(x)surface.The hydrophilic chain of Triton as a Lewis base additive can coordinate with the Ni3+on the NiO_(x)surface which can passivate the interfacial defects and hinder the detrimental reactions at the NiO_(x)/perovskite interface.Additionally,the hydrophobic chain of Triton protrudes from the NiO_(x)surface to prevent moisture from penetrating into the NiO_(x)/perovskite interface.Consequently,the NiO_(x)/Triton-based devices(MAPbI3as absorbing layer) show superior moisture and thermal stability,retaining 88.4% and 64.3% of the initial power conversion efficiency after storage in air(40%-50% relative humidity(RH)) at 25 ℃ for 1070 h and in N2at 85℃ for 800 h,respectively.Moreover,the efficiency increases from 17.59% to 19.89% because of the passivation defect and enhanced hole-extraction capability.Besides,the NiO_(x)/Triton-based PSCs with Cs_(0.05)(MA_(0.15)FA_(0.85))_(0.95)Pb(I_(0.85)Br_(0.15))3perovskite as the light-absorbing layer also exhibits better moisture and thermal stability compared to the control devices,indicating the viability of our strategies.Of particular note,a champion PCE of 22.35% and 20.46% was achieved for small-area(0.1 cm^(2)) and large-area(1.2 cm^(2)) NiO_(x)/Triton-based devices,respectively.展开更多
Electron transport layers(ETLs)are crucial for achieving efficient and stable planar perovskite solar cells(PSCs).Reports on versatile inorganic ETLs using a simple film fabrication method and applicability for both l...Electron transport layers(ETLs)are crucial for achieving efficient and stable planar perovskite solar cells(PSCs).Reports on versatile inorganic ETLs using a simple film fabrication method and applicability for both low-cost planar regular and inverted PSCs with excellent efficiencies(>22%)and high stability are very limited.Herein,we employ a novel inorganic ZnSe as ETL for both regular and inverted PSCs to improve the efficiency and stability using a simple thermal evaporation method.The TiO_(2)-ZnSe-FAPbl_(3)heterojunction could be formed,resulting in an improved charge collection and a decreased carrier recombination further proved through theoretical calculations.The optimized regular PSCs based on TiO_(2)/ZnSe have achieved 23.25%efficiency with negligible hysteresis.In addition,the ZnSe ETL can also effectively replace the unstable bathocuproine(BCP)in inverted PSCs.Consequently,the ZnSe-based inverted device realizes a champion efficiency of 22.54%.Moreover,the regular device comprising the TiO_(2)/ZnSe layers retains 92%of its initial PCE after 10:00 h under 1 Sun continuous illumination and the inverted device comprising the C_(60)/ZnSe layers maintains over 85%of its initial PCE at 85℃for 10:00 h.This highlights one of the best results among universal ETLs in both regular and inverted perovskite photovoltaics.展开更多
Two-dimensional(2D)Ti_(3)C_(2) material has a wide range of photovoltaic applications due to its unique electronic,optical,and plasmonic properties.Herein,we present a series of Ti_(3)C_(2)(0,0.6,0.8;wt%)nanosheets-mo...Two-dimensional(2D)Ti_(3)C_(2) material has a wide range of photovoltaic applications due to its unique electronic,optical,and plasmonic properties.Herein,we present a series of Ti_(3)C_(2)(0,0.6,0.8;wt%)nanosheets-modified P25 nanoparticles as photoanode films for dye-sensitized solar cells(DSSCs).The DSSC based on P25 and 0.6 wt%Ti_(3)C_(2) photoanode achieves a fairly good efficiency(9.22%),which greatly exceeds the counterpart based on the pure P25(7.16%).Benefiting from high light scattering and metallic electrical conductivity of Ti_(3)C_(2) additive,the P25/Ti_(3)C_(2)-based DSSC exhibits a superior behavior of controlling photogenerated charge recombination compared with pure P25 one.展开更多
BiVO_(4)is one of the most promising photoanode materials for photoelectrochemical(PEC)solar energy conversion,but it still suffers from poor photocurrent density due to insufficient light‐harvesting efficiency(LHE),...BiVO_(4)is one of the most promising photoanode materials for photoelectrochemical(PEC)solar energy conversion,but it still suffers from poor photocurrent density due to insufficient light‐harvesting efficiency(LHE),weak photogenerated charge separation efficiency(Φ_(Sep)),and low water oxidation efficiency(Φ_(OX)).Herein,we tackle these challenges of the BiVO_(4)photoanodes using systematic engineering,including catalysis engineering,bandgap engineering,and morphology engineering.In particular,we deposit a NiCoO_(x)layer onto the BiVO_(4)photoanode as the oxygen evolution catalyst to enhance theΦ_(OX)of Fe‐g‐C_(3)N_(4)/BiVO_(4)for PEC water oxidation,and incorporate Fe‐doped graphite‐phase C_(3)N_(4)(Fe‐g‐C_(3)N_(4))into the BiVO_(4)photoanode to optimize the bandgap and surface areas to subsequently expand the light absorption range of the photoanode from 530 to 690 nm,increase the LHE andΦ_(Sep),and further improve the oxygen evolution reaction activity of the NiCoO_(x)catalytic layer.Consequently,the maximum photocurrent density of the as‐prepared NiCoO_(x)/Fe‐g‐C_(3)N_(4)/BiVO_(4)is remarkably boosted from 4.6 to 7.4 mA cm^(−2).This work suggests that the proposed systematic engineering strategy is exceptionally promising for improving LHE,Φ_(Sep),andΦ_(OX)of BiVO_(4)‐based photoanodes,which will substantially benefit the design,preparation,and large‐scale application of next‐generation high‐performance photoanodes.展开更多
Lithium-halogen batteries(LHBs),including lithium iodide(Li-I_(2))and lithium bromide(Li-Br_(2))batteries,are receiving more attention for offering high energy density and excellent kinetic performance.However,LHBs co...Lithium-halogen batteries(LHBs),including lithium iodide(Li-I_(2))and lithium bromide(Li-Br_(2))batteries,are receiving more attention for offering high energy density and excellent kinetic performance.However,LHBs commercialization is seriously hindered by the high solubility of halides,causing lower capacity and poor cyclability.This research covers the fabrication of a highly stable cathode of amorphous carbon coated CMK-3/LiI/LiBr nanocomposite for metal lithium batteries.The nanopores and coated layer can physically trap the dissolution of active materials.The amorphous carbon generated from polyacrylonitrile carries abundant nitrogen heteroatoms for the stable anchorage of halogens and halides via strong chemical adsorption.In addition,iodine can act as a complexing agent with bromine to reduce solvation energy.Consequently,the as-prepared CMK-3/LiI/LiBr/carbon(CIBP)nanocomposite cathode demonstrates an ultra-high reversible capacity of 407.4 mAh/g at the current density of 1.0 C performing up to 300 stable cycles.展开更多
The improvement in the efficiency of inverted perovskite solar cells(PSCs)is significantly limited by undesirable contact at the NiO_(x)/perovskite interface.In this study,a novel microstructure-control technology is ...The improvement in the efficiency of inverted perovskite solar cells(PSCs)is significantly limited by undesirable contact at the NiO_(x)/perovskite interface.In this study,a novel microstructure-control technology is proposed for fabrication of porous NiO_(x)films using Pluronic P123 as the structure-directing agent and acetylacetone(AcAc)as the coordination agent.The synthesized porous NiO_(x)films enhanced the hole extraction efficiency and reduced recombination defects at the NiO_(x)/perovskite interface.Consequently,without any modification,the power conversion efficiency(PCE)of the PSC with MAPbl_(3)as the absorber layer improved from 16.50%to 19.08%.Moreover,the PCE of the device composed of perovskite Cs0.05(MA_(0.15)FA_(0.85))_(0.95)Pb(I_(0.85)Br_(0.15))_(3)improved from 17.49%to 21.42%.Furthermore,the application of the fabricated porous NiO_(x)on fluorine-doped tin oxide(FTO)substrates enabled the fabrication of large-area PSCs(1.2 cm^(2))with a PCE of 19.63%.This study provides a novel strategy for improving the contact at the NiO_(x)/perovskite interface for the fabrication of high-performance large-area perovskite solar cells.展开更多
The waxberry-like mixed-phase TiO_(2)hollow microstructures (WMTHMs) are controllably prepared via a topotactic synthetic method,involving the synthesis of monodispersed Ca TiO_(2)precursors by a solvothermal method a...The waxberry-like mixed-phase TiO_(2)hollow microstructures (WMTHMs) are controllably prepared via a topotactic synthetic method,involving the synthesis of monodispersed Ca TiO_(2)precursors by a solvothermal method and subsequently transforming them into TiO_(2)through a Na_(2)EDTA-assisted ion-exchange process.The ratio of anatase-rutile is adjustable,and the two phases are connected well with each other.WMTHMs are composed of radially aligned nanorods,speeding up the electron transport.The optimum WMTHMs sample shows a specific surface area of 68.05 m^(2)/g and exhibits an excellent light scattering capacity.The cell based on WMTHMs light scattering layer obtained an optimal efficiency of 9.12%.The improvement of cell efficiency is mainly attributed to the high specific surface area,the efficient light scattering,the appropriate ratio of anatase-rutile,the staggered bandgap structure,and the convenient one-dimensional electron transport channel.展开更多
It is with great sadness for us that Professor Wei Jiang, a young and well-known supramolecular chemist, passed away on Sunday25 December 2022. He created a series of supramolecular hosts including Oxatubarenes [1] an...It is with great sadness for us that Professor Wei Jiang, a young and well-known supramolecular chemist, passed away on Sunday25 December 2022. He created a series of supramolecular hosts including Oxatubarenes [1] and Naphthotubes [2] with inner functionalized groups [3–6] and applied them into materials, catalysis,molecular machines and drug recognition and delivery fields [7–10] during his independent research career.展开更多
Selective hydrogenation of C=C and C=O bonds in cinnamaldehyde(CAL)to produce desired products is a challenging task due to the complex conjugate system of the two unsaturated functional groups.In this study,a simple ...Selective hydrogenation of C=C and C=O bonds in cinnamaldehyde(CAL)to produce desired products is a challenging task due to the complex conjugate system of the two unsaturated functional groups.In this study,a simple ball milling method is presented for synthesizing Pt-based single-atom alloy catalysts(SAAs)that can function as a control switch for the selective hydrogenation of CAL into highly valuable products.展开更多
ZIF-67 containing cobalt cation was selected as the research object,and the carbon-containing cobalt matrix nanocomposite(C&Co)was obtained after heat treatment in a nitrogen atmosphere at the appropriate temperat...ZIF-67 containing cobalt cation was selected as the research object,and the carbon-containing cobalt matrix nanocomposite(C&Co)was obtained after heat treatment in a nitrogen atmosphere at the appropriate temperature.The nanostructures and morphologies of the nanocomposite were analyzed by X-ray diffraction,field emission scanning electron microscopy,transmission electron microscopy,and X-ray photoelectron spectroscopy.The electrochemical response was comprehensively characterized by cyclic voltammetry,electrochemical impedance spectroscopy,and Tafel polarization.The electrochemical analysis of the C&Co nanocomposite electrode shows that the electrode has an obvious electrocatalytic activity for the reduction of the triiodide compound.The conversion efficiency of dye-sensitized solar cells prepared with C&Co nanocomposite electrode shows 5.3%under the condition of AM1.5G simulated sunlight irradiation,which shows great application potential in Pt-free electrode materials.展开更多
Dispersing metals from nanoparticles into clusters or single atoms often exhibits unique properties such as the inhibition of structure-sensitive side reactions.Here,we reported the use of ion exchange(IE)methods and ...Dispersing metals from nanoparticles into clusters or single atoms often exhibits unique properties such as the inhibition of structure-sensitive side reactions.Here,we reported the use of ion exchange(IE)methods and direct hydrogen reduction to achieve high dispersion of Co species on zincosilicate.The obtained 2Co/Zn-4-IE catalyst achieved an initial propane conversion of 41.4%at a temperature of 550℃in a 25%propane and 75%nitrogen atmosphere for propane dehydrogenation.Visualization of the presence of Co species within specific rings(alpha-α,beta-βand delta-δ)was obtained by aberration-corrected scanning transmission electron microscopy.A series of Fourier transform infrared spectra confirmed the anchoring of Co by specific hydroxyl groups in zincosilicate and the specific coordination environment of Co and its presence in the rings essentially as a single site.The framework Zn for the modulation of the microenvironment and the presence of Co species as Lewis acid active sites(Co-O4)was also supported by density functional theory calculations.展开更多
The perception of light is crucial for humans to explore the external world.However,challenges of current planar photosensors include inherent limitations in depth of field and field of view.Flexible electronic device...The perception of light is crucial for humans to explore the external world.However,challenges of current planar photosensors include inherent limitations in depth of field and field of view.Flexible electronic devices offer a solution to this issue by allowing adaptation to curved surfaces,ensuring stable interfaces and excellent signal quality.Compared to photoelectric sensors,flexible photosensors based on photothermal conversion can respond to a wider spectrum of light,simplify design processes,and overcome issues such as instability and high toxicity.The review introduces progress on the flexible photosensors based on photothermal conversion,and summarizes the combination of photothermal conversion with pyroelectric,thermoelectric,and thermoresistive effects,allowing for the conversion of light signals into thermal signals and then into electric signals.Additionally,the review outlines the challenges for future research in this field.展开更多
Time-temperature indicator(TTI)technologies enable real-time quality monitoring of perishable products during transportation-storage.Photochromic material-guided TTI offers significant benefits in terms of nondestruct...Time-temperature indicator(TTI)technologies enable real-time quality monitoring of perishable products during transportation-storage.Photochromic material-guided TTI offers significant benefits in terms of nondestructive and convenient visualization.However,photochromic materials with low-temperature-range dependency are rare,limiting the development of cryogenic temperature-responsive TTI methods.This work proposes a novel temperature-gated bicolor photochromic material.Using NaYTiO_(4)as the matrix,which has a native blue color center related to the intrinsic deep trap,Bi^(3+)ions are incorporated to create extremely shallow trap levels(100-230 K)along with an associated longwavelength absorption color center.By combining these two color centers with extended full-spectrum absorption,NaYTiO_(4):Bi^(3+)converts to dark gray upon ultraviolet irradiation below 233 K.With increasing temperature,the trapped electrons in shallow traps are released first,and the color state becomes yellowish until it completely fades back to white above 573 K.The liberation of thermally activated charge carriers is positively correlated with the storage duration and the ambient temperature.For the first time,we realize a TTI method based on photochromic materials at extremely low temperatures,which allows for direct visualization of quality management for cryogenic products without further information extraction and conversion.This work demonstrates the significant ability of photochromic materials as advanced information-recording materials in the next generation of smart TTIs.展开更多
文摘The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.
基金supported by the National Natural Science Foundation of China(12205300(H.S.),12405377(M.H.L))the Postdoctoral Science Foundation of China(2024M763694(M.H.L))+3 种基金the Natural Science Foundation of Hunan Province(2024JJ4027(H.S.))the Postdoctoral Fellowship Program of CPSF under Grant Number GZB20240859(M.H.L)financial support from the Hunan Normal University Program(grant05311204666)financial support from the 2024 Large Instrument Testing Open Fund of Hunan Normal University(24CSY033,24CSY086)。
文摘The electrochemical conversion of nitrate,a widespread water pollutant,into valuable ammonia represents a green and decentralized approach to ammonia synthesis.However,the sluggish multielectronproton coupling path and the low reactive species(nitrate and proton)concentration at the catalyst interface inhibit the efficiency of ammonia production from nitrate reduction reaction(NitRR).Herein,we introduce a novel iron-based tandem catalyst encapsulated by reduced graphene oxide(denoted as Fe-rGO),with a superior ammonia production rate of 47.815 mg h^(-1)mg_(ca)^(t-1)and a high Faraday efficiency(FE)of 96.51%at an applied potential of-0.5 V.It also delivers a robust stability with FE above90%under a current density of 250 mA cm^(-2)for 50 h.In situ X-ray absorption spectroscopy reveals that the FeO_(x)is dynamically translated to Fe~0 site concurrently with the enhancement of the NH_(3)production rate,suggesting the Fe^(0) site as hydrogenation active center.The asymmetric distribution of surface charges of rGO not only enriches nitrate ions at the catalytic interface and promotes the hydrogenation process in NitRR,but also protects the iron species and ensures their stability during electrolysis.The Zn-NO_(3)^(-)battery demonstrates an impressive FE of 88.6%,highlighting its exceptional potential for practical applications.
基金financially supported by the National Key Research and Development Program(No.2022YFC3900905)the National Natural Science Foundation of China(No.52234001)the Science and Technology Planning Project of Hunan Province(No.2018TP1017)
文摘Nickel-rich LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)(NCM)cathodes,pivotal for high-energy-density lithium-ion batteries,face severe challenges from surface residual lithium compounds and hydrofluoric acid(HF)-induced degradation.These issues accelerate capacity fading,exacerbate interfacial polarization,and compromise safety.To address these issues,we proposed a scalable CeF_(3)/H_(3)BO_(3)hybrid coating strategy for LiNi_(0.82)Co_(0.12)Mn_(0.06)O_(2)cathodes.The CeF_(3)nanoparticles served as a robust physical barrier,effectively scavenging HF,while the LiBO_(2)layer derived from H_(3)BO_(3)eliminated residual Li_(2)CO_(3)through chemical conversion and established rapid Li^(+)transport pathways.Dynamic B-O bond reorganization enabled self-repair of coating defects,synergistically suppressing interfacial polarization and maintaining structural integrity.Electrochemical evaluations demonstrated that the hybridcoated cathode achieves 94%capacity retention after 200 cycles at 1C(2.8-4.3 V),significantly outperforming the pristine NCM(56.3%).Additionally,the modified cathode exhibits enhanced air stability,with suppressed H_(2)O/CO_(2)infiltration,and delivers 80%capacity retention after 1000 cycles in practical pouch cells.This work provides a costeffective and industrially viable solution to simultaneously mitigate HF corrosion,residual lithium accumulation,and cathode-electrolyte interphase instability,paving the way for durable high-energy-density batteries.
文摘Dispersing metals from nanoparticles to clusters is often achieved using ligand protection methods,which exhibit unique properties such as suppressing structure-sensitive side reactions.However,this method is limited by the use of different metal precursor salts corresponding to different ligands.An alternative approach,the ion exchange(IE)method,can overcome this limitation to some extent.Nevertheless,there is still an urgent need to address the stabilization of metals(especially precious metals)by using IE method.Here,we reported a Pt cluster catalyst prepared mainly by anchoring Pt atoms via O located near the framework Zn in zincosilicate zeolites and riveted by zeolite surface rings after reduction(reduced Pt/Zn-3-IE).The catalyst can achieve an initial propane conversion of 26%in a pure propane atmosphere at 550℃and shows little deactivation even after 7.5 d of operation.Moreover,the alteration of catalyst by the introduction of framework Zn was also highlighted and interpreted.
基金supported by the National Natural Science Foundation of China(52234001,52201254)the Science and Technology Planning Project of Hunan Province(2018TP1017)+3 种基金the Science,Technoloy and Innovation Project of Changsha Research Institute of Mining and Metallurgy(22-C5CL001)the Young Student Fundamental Research Project of Hunan Natural Science Foundation(2024JJ10036)the Introducing Major Universities and Research Institutions to Jointly Build Innovative Carrier Project of Jining City(2023DYDS022)the Scientific Research Foundation for New Talents in University of Jinan(XRC2406)。
文摘The prelithiated SiO_(x)anode showcases markedly improved Li-storage capabilities compared to its unlithiated counterparts,yet it faces hurdles such as slurry gassing,electrolyte deterioration,and capacity fade attributed to residual alkali and an unstable electrolyte/anode interface.To tackle these challenges,we propose a strategic utilization of residual alkali by creating an in-situ γ-LiAlO_(2)functional layer on the prelithiated SiO_(x)@C anode material.This is accomplished by incorporating a minor amount of Al_(2)O_(3)into the SiO_(x)@C/LiH precursor mixture before the solid-phase prelithiation process.The resulting modified prelithiated SiO_(x)@C anode with in-situ formed electrolyte-isolatingγ-LiAlO_(2)layer exhibits no discernible slurry gas generation within 7 days and substantially mitigates side reactions with the electrolyte,thereby boosting the initial coulombic efficiency and cycling stability of the SiO_(x)@C anode.In half-cell evaluations,the prelithiated SiO_(x)@C anode demonstrates a high Li-storage capacity of 1323 mAh g^(-1)and an impressive initial coulombic efficiency of 91.09%.When assessed in a 3.2 Ah 18,650 cylindrical battery,the prelithiated SiO_(x)@C anode showcases exceptional cyclability,retaining 81% of its capacity after 1000 cycles,underscoring its potential for practical applications.This study introduces a scalable and cost-effective prelithiation technique that propels the development and practical deployment of Si-based anodes by resolving persistent scientific challenges with the use of inexpensive additives.
基金financially supported by the National Natural Science Foundation of China(52201254,52234001,52074177)the National Key Research and Development Program(2022YFC3900905)+3 种基金the Natural Science Foundation of Shandong Province(ZR2020QE012,ZR2020MB090,ZR2023ME155,ZR2023ME085)the Scientific Research Foundation for New Talents in University of Jinan(XRC2406)the project of “20 Items of University”of Jinan(202228046)the Introducing Major Universities and Research Institutions to Jointly Build Innovative Carrier Project of Jining City(2023DYDS022)。
文摘The Li-CO_(2)battery has been highly rated as an intriguing technique for balancing the carbon cycle for years,but it is still significantly challenged by the obstacles such as limited reversibility,sluggish kinetics,and poor energy efficiency.Hence,the design and development of advance catalysts that can enhance the kinetics and reversibility of the CO_(2)electrochemical cycling reactions are considered the imperative tasks.Transition metal-based catalysts are widely considered appealing owing to their unfilled dorbitals,rich and adjustable valences,as well as processibility.In this review,the working mechanism and the key issues of the CO_(2)electrochemical cycling reaction are discussed first.Then the strategies for composition and structure design of different type of transition metal-based catalysts are highlighted,including their benefits,limitations,and the ways to implement these strategies.Finally,based on the pioneering research,the perspectives on the challenges and key points for the future development of cathode catalyst are proposed.
基金financially supported by the National Natural Science Foundation of China(No.21825503)。
文摘Covalent crosslinking points within thermosets generally result in excellent mechanical properties and solvent resistance yet lead to limited degradability and recyclability.Those thermosets become degradable or recyclable if crosslinking points are cleavable or reversible.Following this principle,we report a kind of polyurea-urethane thermoset with borate ester as its crosslinking point to enable a controllable decrosslinking in response to acetate acid.Such a thermoset presents remarkable mechanical properties as well as outstanding solvent resistance capability,due to the high crosslinking density and intermolecular hydrogen bonding.Furthermore,the de-crosslinked product can be reporcessed to generate a brand new thermoplastic material.
基金supported by the National Key Research and Development Program of China(2018YFA0208701)the National Natural Science Foundation of China(21773308)+7 种基金the Research Funds of Renmin University of China(2017030013,201903020 and 20XNH059)the Fundamental Research Funds for Central Universities(China)supported by the Solar Energy Research Institute of Singapore(SERIS) at the National University of Singapore(NUS)supported by NUSthe National Research Foundation Singapore(NRF)the Energy Market Authority of Singapore(EMA)the Singapore Economic Development Board(EDB)the financial support from the China Scholarship Council(CSC) funding。
文摘The presence of defects and detrimental reactions at NiO_(x)/perovskite interface extremely limit the efficiency performance and long-term stability of the perovskite solar cells(PSCs) based on NiO_(x).Herein,an amphipathic molecule Triton X100(Triton) is modified on the NiO_(x)surface.The hydrophilic chain of Triton as a Lewis base additive can coordinate with the Ni3+on the NiO_(x)surface which can passivate the interfacial defects and hinder the detrimental reactions at the NiO_(x)/perovskite interface.Additionally,the hydrophobic chain of Triton protrudes from the NiO_(x)surface to prevent moisture from penetrating into the NiO_(x)/perovskite interface.Consequently,the NiO_(x)/Triton-based devices(MAPbI3as absorbing layer) show superior moisture and thermal stability,retaining 88.4% and 64.3% of the initial power conversion efficiency after storage in air(40%-50% relative humidity(RH)) at 25 ℃ for 1070 h and in N2at 85℃ for 800 h,respectively.Moreover,the efficiency increases from 17.59% to 19.89% because of the passivation defect and enhanced hole-extraction capability.Besides,the NiO_(x)/Triton-based PSCs with Cs_(0.05)(MA_(0.15)FA_(0.85))_(0.95)Pb(I_(0.85)Br_(0.15))3perovskite as the light-absorbing layer also exhibits better moisture and thermal stability compared to the control devices,indicating the viability of our strategies.Of particular note,a champion PCE of 22.35% and 20.46% was achieved for small-area(0.1 cm^(2)) and large-area(1.2 cm^(2)) NiO_(x)/Triton-based devices,respectively.
基金supported by the Solar Energy Research Institute of Singapore(SERIS)at the National University of Singapore(NUS).SERIS is supported by NUS,the National Research Foundation Singapore(NRF),the Energy Market Authority of Singapore(EMA),and the Singapore Economic Development Board(EDB)support from the Science and Engineering Research Council of Singapore with Grant No.A1898b0043Singapore NRF CRP Grant No.NRF-CRP24-2020-0002.
文摘Electron transport layers(ETLs)are crucial for achieving efficient and stable planar perovskite solar cells(PSCs).Reports on versatile inorganic ETLs using a simple film fabrication method and applicability for both low-cost planar regular and inverted PSCs with excellent efficiencies(>22%)and high stability are very limited.Herein,we employ a novel inorganic ZnSe as ETL for both regular and inverted PSCs to improve the efficiency and stability using a simple thermal evaporation method.The TiO_(2)-ZnSe-FAPbl_(3)heterojunction could be formed,resulting in an improved charge collection and a decreased carrier recombination further proved through theoretical calculations.The optimized regular PSCs based on TiO_(2)/ZnSe have achieved 23.25%efficiency with negligible hysteresis.In addition,the ZnSe ETL can also effectively replace the unstable bathocuproine(BCP)in inverted PSCs.Consequently,the ZnSe-based inverted device realizes a champion efficiency of 22.54%.Moreover,the regular device comprising the TiO_(2)/ZnSe layers retains 92%of its initial PCE after 10:00 h under 1 Sun continuous illumination and the inverted device comprising the C_(60)/ZnSe layers maintains over 85%of its initial PCE at 85℃for 10:00 h.This highlights one of the best results among universal ETLs in both regular and inverted perovskite photovoltaics.
基金financially supported by the National Natural Science Foundation of China(No.21965013)the Natural Science Foundation of Hainan Province(Nos.220RC590 and 521QN239)。
文摘Two-dimensional(2D)Ti_(3)C_(2) material has a wide range of photovoltaic applications due to its unique electronic,optical,and plasmonic properties.Herein,we present a series of Ti_(3)C_(2)(0,0.6,0.8;wt%)nanosheets-modified P25 nanoparticles as photoanode films for dye-sensitized solar cells(DSSCs).The DSSC based on P25 and 0.6 wt%Ti_(3)C_(2) photoanode achieves a fairly good efficiency(9.22%),which greatly exceeds the counterpart based on the pure P25(7.16%).Benefiting from high light scattering and metallic electrical conductivity of Ti_(3)C_(2) additive,the P25/Ti_(3)C_(2)-based DSSC exhibits a superior behavior of controlling photogenerated charge recombination compared with pure P25 one.
基金Natural Science Foundation of China,Grant/Award Number:22108042Guangzhou(202201020147)。
文摘BiVO_(4)is one of the most promising photoanode materials for photoelectrochemical(PEC)solar energy conversion,but it still suffers from poor photocurrent density due to insufficient light‐harvesting efficiency(LHE),weak photogenerated charge separation efficiency(Φ_(Sep)),and low water oxidation efficiency(Φ_(OX)).Herein,we tackle these challenges of the BiVO_(4)photoanodes using systematic engineering,including catalysis engineering,bandgap engineering,and morphology engineering.In particular,we deposit a NiCoO_(x)layer onto the BiVO_(4)photoanode as the oxygen evolution catalyst to enhance theΦ_(OX)of Fe‐g‐C_(3)N_(4)/BiVO_(4)for PEC water oxidation,and incorporate Fe‐doped graphite‐phase C_(3)N_(4)(Fe‐g‐C_(3)N_(4))into the BiVO_(4)photoanode to optimize the bandgap and surface areas to subsequently expand the light absorption range of the photoanode from 530 to 690 nm,increase the LHE andΦ_(Sep),and further improve the oxygen evolution reaction activity of the NiCoO_(x)catalytic layer.Consequently,the maximum photocurrent density of the as‐prepared NiCoO_(x)/Fe‐g‐C_(3)N_(4)/BiVO_(4)is remarkably boosted from 4.6 to 7.4 mA cm^(−2).This work suggests that the proposed systematic engineering strategy is exceptionally promising for improving LHE,Φ_(Sep),andΦ_(OX)of BiVO_(4)‐based photoanodes,which will substantially benefit the design,preparation,and large‐scale application of next‐generation high‐performance photoanodes.
基金the financial support by the Research Foundation of Hunan Education Committee of China(No.21B0067)Natural National Science Foundation of China(No.22278197).
文摘Lithium-halogen batteries(LHBs),including lithium iodide(Li-I_(2))and lithium bromide(Li-Br_(2))batteries,are receiving more attention for offering high energy density and excellent kinetic performance.However,LHBs commercialization is seriously hindered by the high solubility of halides,causing lower capacity and poor cyclability.This research covers the fabrication of a highly stable cathode of amorphous carbon coated CMK-3/LiI/LiBr nanocomposite for metal lithium batteries.The nanopores and coated layer can physically trap the dissolution of active materials.The amorphous carbon generated from polyacrylonitrile carries abundant nitrogen heteroatoms for the stable anchorage of halogens and halides via strong chemical adsorption.In addition,iodine can act as a complexing agent with bromine to reduce solvation energy.Consequently,the as-prepared CMK-3/LiI/LiBr/carbon(CIBP)nanocomposite cathode demonstrates an ultra-high reversible capacity of 407.4 mAh/g at the current density of 1.0 C performing up to 300 stable cycles.
基金supported by the National Key Research and Development Program of China(grant no.2018YFA0208701)National Natural Science Foundation of China(grant no.21773308)+6 种基金Research Funds of Renmin University of China(grant nos.2017030013,201903020,and 20XNH059)Fundamental Research Funds for Central Universities(China)supported by the Solar Energy Research Institute of Singapore(SERIS)at the National University of Singapore(NUS)supported by NUS,the National Research Foundation Singapore(NRF),the Energy Market Authority of Singapore(EMA),and the Singapore Economic Development Board(EDB)the experimental support from Suzhou Fangsheng FS-300funding from Deutsche Forschungsge-meinschaft(DFG)via Germany's Excellence Strategy-EXC 2089/1-390776260(e-conversion)as well as from TUM.solar in the context of the Bavarian Collaborative Research Project Solar Technologies Go Hybrid(SoITech)the China Scholarship Council(CSC)funding
文摘The improvement in the efficiency of inverted perovskite solar cells(PSCs)is significantly limited by undesirable contact at the NiO_(x)/perovskite interface.In this study,a novel microstructure-control technology is proposed for fabrication of porous NiO_(x)films using Pluronic P123 as the structure-directing agent and acetylacetone(AcAc)as the coordination agent.The synthesized porous NiO_(x)films enhanced the hole extraction efficiency and reduced recombination defects at the NiO_(x)/perovskite interface.Consequently,without any modification,the power conversion efficiency(PCE)of the PSC with MAPbl_(3)as the absorber layer improved from 16.50%to 19.08%.Moreover,the PCE of the device composed of perovskite Cs0.05(MA_(0.15)FA_(0.85))_(0.95)Pb(I_(0.85)Br_(0.15))_(3)improved from 17.49%to 21.42%.Furthermore,the application of the fabricated porous NiO_(x)on fluorine-doped tin oxide(FTO)substrates enabled the fabrication of large-area PSCs(1.2 cm^(2))with a PCE of 19.63%.This study provides a novel strategy for improving the contact at the NiO_(x)/perovskite interface for the fabrication of high-performance large-area perovskite solar cells.
基金financially supported by the National Natural Science Foundation of China (No.21965013)the Natural Science Foundation of Hainan Province (No.220RC590)the Graduate Student Research and Innovation Program of Hainan Province (No.hsyx2019-17)。
文摘The waxberry-like mixed-phase TiO_(2)hollow microstructures (WMTHMs) are controllably prepared via a topotactic synthetic method,involving the synthesis of monodispersed Ca TiO_(2)precursors by a solvothermal method and subsequently transforming them into TiO_(2)through a Na_(2)EDTA-assisted ion-exchange process.The ratio of anatase-rutile is adjustable,and the two phases are connected well with each other.WMTHMs are composed of radially aligned nanorods,speeding up the electron transport.The optimum WMTHMs sample shows a specific surface area of 68.05 m^(2)/g and exhibits an excellent light scattering capacity.The cell based on WMTHMs light scattering layer obtained an optimal efficiency of 9.12%.The improvement of cell efficiency is mainly attributed to the high specific surface area,the efficient light scattering,the appropriate ratio of anatase-rutile,the staggered bandgap structure,and the convenient one-dimensional electron transport channel.
文摘It is with great sadness for us that Professor Wei Jiang, a young and well-known supramolecular chemist, passed away on Sunday25 December 2022. He created a series of supramolecular hosts including Oxatubarenes [1] and Naphthotubes [2] with inner functionalized groups [3–6] and applied them into materials, catalysis,molecular machines and drug recognition and delivery fields [7–10] during his independent research career.
基金financially supported by the National key Research and Development Program Nanotechnology Specific Project(No.2020YFA0210900)the Science and Technology Key Project of Guangdong Province,China(No.2020B010188002)+6 种基金Guangdong Natural Science Funds for Distinguished Young Scholar(No.2022B1515020035)Guangdong Provincial Key R&D Programme(No.2019B110206002)the National Natural Science Foundation of China(Nos.22078371,21938001 and 21961160741)Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(No.2017BT0IC102)the NSF of Guangdong Province(No.2020A1515011141)the Science and Technology Project of Guangzhou City,China(No.202102020461)Special funding for"Guangxi Bagui Scholars"。
文摘Selective hydrogenation of C=C and C=O bonds in cinnamaldehyde(CAL)to produce desired products is a challenging task due to the complex conjugate system of the two unsaturated functional groups.In this study,a simple ball milling method is presented for synthesizing Pt-based single-atom alloy catalysts(SAAs)that can function as a control switch for the selective hydrogenation of CAL into highly valuable products.
基金supported by the National Natural Science Foundation of China(21965013)Hainan Provincial Natural Science Foundation(521CXTD438)Hainan Province Postdoctoral Research Funding Project(RZ2300005520)
文摘ZIF-67 containing cobalt cation was selected as the research object,and the carbon-containing cobalt matrix nanocomposite(C&Co)was obtained after heat treatment in a nitrogen atmosphere at the appropriate temperature.The nanostructures and morphologies of the nanocomposite were analyzed by X-ray diffraction,field emission scanning electron microscopy,transmission electron microscopy,and X-ray photoelectron spectroscopy.The electrochemical response was comprehensively characterized by cyclic voltammetry,electrochemical impedance spectroscopy,and Tafel polarization.The electrochemical analysis of the C&Co nanocomposite electrode shows that the electrode has an obvious electrocatalytic activity for the reduction of the triiodide compound.The conversion efficiency of dye-sensitized solar cells prepared with C&Co nanocomposite electrode shows 5.3%under the condition of AM1.5G simulated sunlight irradiation,which shows great application potential in Pt-free electrode materials.
文摘Dispersing metals from nanoparticles into clusters or single atoms often exhibits unique properties such as the inhibition of structure-sensitive side reactions.Here,we reported the use of ion exchange(IE)methods and direct hydrogen reduction to achieve high dispersion of Co species on zincosilicate.The obtained 2Co/Zn-4-IE catalyst achieved an initial propane conversion of 41.4%at a temperature of 550℃in a 25%propane and 75%nitrogen atmosphere for propane dehydrogenation.Visualization of the presence of Co species within specific rings(alpha-α,beta-βand delta-δ)was obtained by aberration-corrected scanning transmission electron microscopy.A series of Fourier transform infrared spectra confirmed the anchoring of Co by specific hydroxyl groups in zincosilicate and the specific coordination environment of Co and its presence in the rings essentially as a single site.The framework Zn for the modulation of the microenvironment and the presence of Co species as Lewis acid active sites(Co-O4)was also supported by density functional theory calculations.
基金financially supported by the Beijing Natural Science Foundation(No.2242037)the National Natural Science Foundation of China(No.22005336)。
文摘The perception of light is crucial for humans to explore the external world.However,challenges of current planar photosensors include inherent limitations in depth of field and field of view.Flexible electronic devices offer a solution to this issue by allowing adaptation to curved surfaces,ensuring stable interfaces and excellent signal quality.Compared to photoelectric sensors,flexible photosensors based on photothermal conversion can respond to a wider spectrum of light,simplify design processes,and overcome issues such as instability and high toxicity.The review introduces progress on the flexible photosensors based on photothermal conversion,and summarizes the combination of photothermal conversion with pyroelectric,thermoelectric,and thermoresistive effects,allowing for the conversion of light signals into thermal signals and then into electric signals.Additionally,the review outlines the challenges for future research in this field.
基金supported by the National Key Research and Development Program of China(2023YFD1700903)the Scientific Research Fund of the Hunan Provincial Education Department(24A0073)+1 种基金the Young Talent Lift Program of Hunan Normal University(2024QNTJ05)the National Natural Science Foundation of China(12204197)。
文摘Time-temperature indicator(TTI)technologies enable real-time quality monitoring of perishable products during transportation-storage.Photochromic material-guided TTI offers significant benefits in terms of nondestructive and convenient visualization.However,photochromic materials with low-temperature-range dependency are rare,limiting the development of cryogenic temperature-responsive TTI methods.This work proposes a novel temperature-gated bicolor photochromic material.Using NaYTiO_(4)as the matrix,which has a native blue color center related to the intrinsic deep trap,Bi^(3+)ions are incorporated to create extremely shallow trap levels(100-230 K)along with an associated longwavelength absorption color center.By combining these two color centers with extended full-spectrum absorption,NaYTiO_(4):Bi^(3+)converts to dark gray upon ultraviolet irradiation below 233 K.With increasing temperature,the trapped electrons in shallow traps are released first,and the color state becomes yellowish until it completely fades back to white above 573 K.The liberation of thermally activated charge carriers is positively correlated with the storage duration and the ambient temperature.For the first time,we realize a TTI method based on photochromic materials at extremely low temperatures,which allows for direct visualization of quality management for cryogenic products without further information extraction and conversion.This work demonstrates the significant ability of photochromic materials as advanced information-recording materials in the next generation of smart TTIs.
