Interfacial engineering through lead binding using crown ethers in perovskite solar cells

In the domain of perovskite solar cells(PSCs),the imperative to reconcile impressive photovoltaic performance with lead-related issue and environmental stability has driven innovative solutions.This study pioneers an approach that not only rectifies lead leakage but also places paramount importance on the attainment of rigorous interfacial passivation.Crown ethers,notably benzo-18-crown-6-ether(B18C6),were strategically integrated at the perovskite-hole transport material interface.Crown ethers exhibit a dual role:efficiently sequestering and immobilizing Pb^(2+)ions through host-guest complexation and simultaneously establishing a robust interfacial passivation layer.Selected crown ether candidates,guided by density functional theory(DFT)calculations,demonstrated proficiency in binding Pb2+ions and optimizing interfacial energetics.Photovoltaic devices incorporating these materials achieved exceptional power conversion efficiency(PCE),notably 21.7%for B18C6,underscoring their efficacy in lead binding and interfacial passivation.Analytical techniques,including time-of-flight secondary ion mass spectrometry(ToF-SIMS),ultraviolet photoelectron spectroscopy(UPS),time-resolved photoluminescence(TRPL),and transient absorption spectroscopy(TAS),unequivocally affirmed Pb^(2+)ion capture and suppression of non-radiative recombination.Notably,these PSCs maintained efficiency even after enduring 300 h of exposure to 85%relative humidity.This research underscores the transformative potential of crown ethers,simultaneously addressing lead binding and stringent interfacial passivation for sustainable PSCs poised to commercialize and advance renewable energy applications.

Li^(+)-ion bound crown ether functionalization enables dual promotion of dynamics and thermodynamics for ambient ammonia synthesis

Electrosynthesis of ammonia from the reduction of nitrogen is still confronted with the limited supply of gas reactant in dynamics as well as high activation barrier in thermodynamics.Unfortunately,despite tremendous efforts devoted to electrocatalysts themselves,they still fail to tackle the above two challenges simultaneously.Herein,we employ a heterogeneous catalyst adlayer-composed of crown ethers associated with Li^(+)ions-to achieve the dual promotion of dynamics and thermodynamics for ambient ammonia synthesis.Dynamically,the bound Li^(+)ions interact with the strong quadrupole moment of nitrogen,and trigger considerable reactant flux toward the catalyst.Thermodynamically,Li^(+)associated with the oxygen of crown ether achieves a higher density of states at the Fermi level for the catalyst,enabling effortless electron transfer from the catalysts to nitrogen and thus greatly reducing the activation barrier.As expected,the proof-of-concept system achieves an ammonia yield rate of 168.5μg h^(-1)mg^(-1)and a Faradaic efficiency of 75.3%at-0.3 V vs.RHE.This system-level approach opens up pathways for tackling the two key challenges that have limited the field of ammonia synthesis.

SILICA-BOUND CROWN ETHERS PLATINUM COMPLEX AS HYDROSILYLATION CATALYST

Silica-bound 15-Crown-5, 18-Crown-6 with a spacer of propyloxymethyl and their platinum complexes have been synthesized. It was found that they were efficient catalysts for the hydrosilylation of olefms with triethoxysilane in the temperature range of 60 to 130 ℃.

NETWORK CROWN ETHER POLYMERS WITH CENTRIC FUNCTIONAL GROUP (Ⅳ) SYNTHESIS OF NETWORK CROWN ETHER POLYMER WITH PENDANT DIETHYLAMINO THIAALKYL GROUP AND ITS PLATINUM COMPLEX

The title polymer was prepared from 5-diethylamino-3-thia-pentyl glycidyl ether anddiethylene glycol bisglycidyl ether via ring-opening copolymerization. It was found that thisreaction could be catalyzed by sodium, but not Lewis acid. The obtained polymer can coordinatewith platinum compound, and the platinum complex is a new kind of catalyst for thehydrosilylation of olefins with triethoxysilane.

STUDIES ON CROWN ETHER CYANINE DYES(XI)THE SYNTHESIS OF BENZOTELLURAZOLE CROWN ETHER CYANINE DYES

Three methods for synthesis of benzotellurazole crown ether(6)are described.The cyanine dye(8)can be easily obtained by treating(6) with CH_3I and CH(OEt)_3.

Applications of Crown Ether Cross-Linked Chitosan for the Analysis of Lead and Cadmium in Environmental Water Samples

A new type of crown ether cross-linked chitosan was synthesized by the reaction of chitosan with 4,4′-dibromodibenzo-18-crown-6 (Br-DBC). Its token structure was analyzed with FT-IR and NMR and the adsorption behaviors for lead and cadmium in environmental water samples by FAAS were studied. In addition the best analysis conditions were discussed and the adsorption mechanism was explained. As the enrichment factor is above 100, both recoveries are 94%–106%, the detection limits of lead and cadmium are 0.5μg·L?1 and 0.04 μg·L?1 and the relatively standard deviations of lead and cadmium are 3.1% and 2.8% respectively, this new method was successfully applied to the determination of environmental water samples. This method is fast and simple and it greatly enhances the determination ability of FAAS for lead and cadmium.

Preparation of Copolymer of Salen-crown Ether Complexes and its Catalytic Activation for Molecular Oxygen

A new stable salen Schiff base cobalt and crown ether sodium complex （SalCo-NaB18C6） was prepared through copolymerization. This copolymer complex was applied to catalytic oxidation of hydrocarbon compound with molecular oxygen without reductant, which was shown the higher activity and selectivity for ketone, and reused effectively.

SIDE CHAIN LIQUID CRYSTALLINE POLYSILOXANES CONTAINING CROWN ETHER AND BENZYL ETHER MOIETIES

Two kinds of side chain liquid crystalline polysiloxanes containing crown ether and benzyl ether were synthesized and characterized by optical polarization microscopy. Both the monomeric liquid crystals and polymeric liquid crystals show smectic phases.

Synthesis of New Aza-crown Ethers Containing Pyridine Ring and their Liquid Membrane Transport of Alkali Cations

Five new aza-crown ethers have been prepared by the condensation of 2,6-bis[(2-formylphenyl)oxymethyl] pyridine with different diamino compounds in hot methanol, the bis-Schiff bases without isolation were reduced with NaBH4 to afford the corresponding aza-crown ethers. The liquid membrane transport or alkali cations using the five new macrocycles as the ion-carriers was also studied.

Studies on the Synthesis and Complexing Behavior of Crown Ethers with External Coordination Center

The synthesis, characterization of five ditopic or tritopic crown compounds were reported in this paper together with the preparation of the corresponding hetero-dinuclear and hetero-trinuclear complexes with different metal cations.

Suppressing Li Dendrites via Electrolyte Engineering by Crown Ethers for Lithium Metal Batteries

Electrolyte engineering is considered as an effective strategy to establish stable solid electrolyte interface(SEI),and thus to suppress the growth of lithium dendrites.In a recent study reported in Advanced Functional Materials by Ma group,discovered that strong coordination force could be founded between 15-Crown-5 ether(15-C-5) and Li+,which facilitates the crown ether(15-C-1) to participate in the solvation structure of Li+ in the electrolyte for the same purpose.Such a novel strategy might impact the design of highperformance and safe lithium metal batteries(LMB s).

Spectral Properties of Extracted Complexes of MetalPicrates with Crown Ethers

The investigation on UV-visible spectra of species formed by extracting some metal picrates with benzo-15-crown-5(B15C5) and dibenzo-18-crown-6(DB18C6) verified that there are some interactions of picrate anion with K+, Na+ and rare earth ions in loaded organic phase. By the study of the charge transfer band and absorption spectra of picrate anion, it can be determined whether an ion pair has been formed and either a 1 : 1 contact ion pair or a 1 : 2 crown-separated ion pair involved in organic phase can be distinguished for an ion-pair extraction.

Synthesis, Characterization and Fluorescence of Rare earth Nitrate Complexes with Triaza-crown Ether Derivative

Four new complexes of rare earths with a triaza crown ether (L) derived from N 3O 2 macro cycle 1,12,15 triaza 3, 4: 9,10 dibenzo 5, 8 dioxacycloheptadecane were synthesized and characterized by elemental analysis, IR, molar conductance, TG DTA analysis and fluorescence spectra. The composition of the complexes determined as [RE(NO 3) 3L·3H 2O]·H 2O (RE=Sm, Eu, Tb and Dy). It is found that Sm 3+ , Eu 3+ , Tb 3+ and Dy 3+ complexes all show strong fluorescence emission in the solid state. Among these complexes, Tb 3+ complex has the strongest luminescence intensity. It shows that the ligand L triplet state energy matches 5D 4 energy level of Tb 3+ . In the Eu 3+ complex, η ( 5D 0→ 7F 2/ 5D 0→ 7F 1) is 2.6, which indicates that Eu 3+ locates at the asymmetric coordination field.

Synthesis and Properties of New-type Troponoid Dithio-Crown Ethers

Condensation of 3,7-dichloromethyl-5-isopropyl-2-methoxytropane 4 with bis (mercaptoethyl) ether 5a and mono, di, and tri-ethylene glycol bis(mercaptoethyl) ethers 5b-5d gave troponoid-annexed dithiocrown ethers 6a-6d. Compounds 6a-6d have selective and reversible mercury salt capturing ability.

Liquid Membrane Transport Behavior of Functional Substituted Crown Ethers for Amino Acids

Three functional substituted crown ethers were synthesized as liquid membrane transport carriers for amino acids. The result obtained shows that this kind of ditopic ligands can transport sodium salt of amino acids in good rate value especially the one with two pyridinyl groups as binding site outside the macrocycle.

Studies on Rare Earth Complexes with Crown Ether (ⅩⅩⅣ)——Synthesis and Characterization of Complexes of Lanthanide Isothiocyanates with Dibenzo-30-crown-10

Introduction The study of metal complexes with the crown ether is a quite interesting research field, but the research has mainly focused on the metal complexes with some crown ethers with a relatively small cavity such as 12-crown-4, 15-crown-5 and 18- crown-6 as well as their derivatives. Crown ethers with a larger cavity contain more oxygen atoms, so they have the ability to form the complexes of a higher co-

SYNTHESIS OF MAIN CHAIN LIQUID CRYSTALLINE COPOLYESTERS WITH X-SHAPED TWO-DIMENSIONAL MESOGENIC UNIT AND CROWN ETHER CYCLE

A novel series of main chain liquid crystalline copolyesters with X-shaped two-dimensional mesogenic unit and crown ether cycle of cis-4,4＇-bis（4-hydroxyphenylazo） dibenzo-18-crown-6 was prepared via solution condensation polymerization from 4,4＇-（a;arhexanedioyloxy） dibenzoyl dichloride （MI）, 2,5-bis（p-octyloxybenzoyloxy） hydro-quinone （M2） and cis-4,4＇-bis（4-hydroxyphenylazo） dibenzo-18-crown-6 （M3）. Monomer MI was synthesized by esterification and substitution of adipoyl chloride with p-hydroxybenzoic acid, monomer M2 was synthesized by esterfication and reduction reaction of 2,5-dihydroxybenzoquinone and p-octanoxybenzoyl chloride and monomer M3 was synthesized by diazotization and coupling reaction of cis-diaminodibenzo-18-crown-6 with phenol. The molecular weights of copolyesters are not high, and the intrinsic viscosity [η] of copolyesters ranges from 0.25-0.35. The monomers＇ structures were identified by using elemental analysis, IR, UV, ^1H-NMR, MS, etc. All the copolyesters are yellowish powders and insoluble in THF and CHC13 at room temperature except cPg. The properties of copolyesters were investigated by using GPC, [η] , DSC, TG, WAXD and POM. It was found that all the copolyesters entered into liquid crystal phase when they were heated to above their melting temperature （Tin）. The typical smectic and nematic phase texture can be observed on POM. Their mesophase transition temperature and thermal stability change regularly with varying the content of cis-4,4＇-bis（4-hydroxyphenylazo） dibenzo-18-crown-6 unit in the copolyesters.

Bis Crown Ethers( Ⅸ)——Caesium Selective PVC Membrane Electrodes Based on Schif f Base Type of Bis Crown Ethers

Recently, much attention has been focused on the use of neutral carrier species as membrane components to extract ions from aqueous solution into a hydrophobic membrane phase. Some potassium-or caesium-selective electrodes based on bis-benzo-15-crown-5 or bis-benzo-18-crown-6 containing ester or other linkage were prepared by K. Kimura and K. W. Fung. The selective coefficients K;, K;,or K;, K were 2.6×10;, 1.9×10;and 1.7×10;, respectively.

SYNTHESIS OF LIQUID CRYSTALLINE COPOLYESTERS WITH T-SHAPED TWO-DIMENSIONAL MESOGENIC UNIT AND CROWN ETHER CYCLE

A novel series of liquid crystalline copolyesters with T-shaped two-dimensional mesogenic unit and crown ether cycle of cis-4,4′-bis(4-hydroxyphenylazo)dibenzo-18-crown-6 was prepared via solution condensation polymerization from 4,4′-(α,ω-hexanedioyloxy)dibenzoyl dichloride(M_1),2-(4′-ethoxyphenyl)hydroquinone(M_2)and cis-4,4′-bis(4- hydroxyphenylazo)dibenzo-18-crown-6(M_3).The molecular weights of copolyesters are not high,and the intrinsic viscosity [η]of copolyesters ranges from 0.29-0.43.The monomers ...