This research aims to study the bio-adsorption process of two dyes,Cibacron Green H3G(CG-H3G)and Terasil Red(TR),in a single system and to bring them closer to the industrial textile discharge by a binary mixture of t...This research aims to study the bio-adsorption process of two dyes,Cibacron Green H3G(CG-H3G)and Terasil Red(TR),in a single system and to bring them closer to the industrial textile discharge by a binary mixture of two dyes(TR+CG-H3G).The Cockle Shell(CS)was used as a natural bio-adsorbent.The characterizations of CS were investigated by Fourier transform infrared(FTIR),X-ray diffraction(XRD),scanning electron microscopy(SEM),energy-dispersive X-ray spectroscopy(EDX)and Brunauer–Emmett–Teller(BET).The adsorption potential of Cockle Shells was tested in two cases(single and binary system)and determined by:contact time(0–60 min),bio-adsorption dose(3–15 g/L),initial concentration(10–300 mg/L),temperature(22–61°C)and pH solution(2–12).The study of bio-adsorption(equilibrium and kinetics)was conducted at 22°C.The kinetic studies demon-strated that a pseudo-second-order adsorption mechanism had a good correlation coefficient(R2≥0.999).The Langmuir isotherm modeling provided a well-defined description of TR and CG-H3G bio-adsorption on cockle shells,exhibiting maximum capacities of 29.41 and 3.69 mg/g respectively at 22°C.The thermodynamic study shows that the reaction between the TR,CG-H3G dyes molecules and the bio-adsorbent is exothermic,spontaneous in the range of 22–31°C with the aleatory character decrease at the solid-liquid interface.The study of selectivity in single and binary systems has been performed under optimal operating conditions using the industrial textile rejection pH(pH=6.04).CG-H3G dye is found to have a higher selectivity than TR in single(0–60 min)and binary systems with a range of 6–45 min,as shown by the selectivity measurement.It was discovered that CS has the capability to remove both CG-H3G and TR dyes in both simple and binary systems,making it a superior bio-adsorbent.展开更多
The potential of 2-amino-1-propanol(AP)as a novel depressant in selectively floating ilmenite from titanaugite under weakly acidic conditions was investigated.Micro-flotation results show that AP significantly reduces...The potential of 2-amino-1-propanol(AP)as a novel depressant in selectively floating ilmenite from titanaugite under weakly acidic conditions was investigated.Micro-flotation results show that AP significantly reduces the recovery of titanaugite while having no evident impact on ilmenite flotation.Subsequent bench-scale flotation tests further confirm a remarkable improvement in separation efficiency upon the introduction of AP.Contact angle and adsorption tests reveal a stronger affinity of AP towards the titanaugite surface in comparison to ilmenite.Zeta potential measurements and X-ray photoelectron spectroscopy(XPS)analyses exhibit favorable adsorption characteristics of AP on titanaugite,resulting from a synergy of electrostatic attraction and chemical interaction.In contrast,electrostatic repulsion hinders any significant interaction between AP and the ilmenite surface.These findings highlight the potential of AP as a highly efficient depressant for ilmenite flotation,paving the way for reduced reliance on sulfuric acid in the industry.展开更多
Radioactive microspheres have demonstrated excellent therapeutic effects and good tolerance in the treatment of unresectable primary and secondary liver malignancies.This is attributed to precise embolization and pote...Radioactive microspheres have demonstrated excellent therapeutic effects and good tolerance in the treatment of unresectable primary and secondary liver malignancies.This is attributed to precise embolization and potent anti-tumor effect.However,certain limitations such as unstable loading,perfusion stasis,heterogeneous distribution,ectopic distribution,and insufficient dosage,restrict their clinical application.Herein,a novel personalized Y-90 carbon microsphere with high uniformity,high specific activity and high availability(^(90)Y-HUACM)is presented.It is synthesized through planar molecular complex adsorption and chemical deposition solidification.^(90)Y-HUACM exhibited controllable size,excellent biocompatibility,outstanding in vitro and in vivo stability.The radiolabeling efficiency of Y-90 exceeded 99%and the leaching rate of Y-90 is far below 0.1%.Furthermore,the excellent anti-tumor effect,nuclide loading stability,anti-reflux characteristics,precise embolization,and biosafety of^(90)Y-HUACM were validated in a rabbit VX2liver tumor model.In summary,this new,high-performance,and customizable radioactive microsphere provides a superior choice for selective internal radiation treatment of advanced liver cancer is expected to be rapidly applied in clinical practice.展开更多
Base-catalyzed nucleophilic substitution reactions ofβ-ketonitrile with azodicarboxylates have been developed.A series of disubstituted C—N coupling products were obtained in good to excellent yields under Et_(3)N c...Base-catalyzed nucleophilic substitution reactions ofβ-ketonitrile with azodicarboxylates have been developed.A series of disubstituted C—N coupling products were obtained in good to excellent yields under Et_(3)N catalysis.Monosubstitu-tion C—N bond formation reaction catalyzed by K_(2)CO_(3) also gave novel enol-based target products.This method is simple and mild,with good chemoselectivity,excellent substrate compatibility and tolerance for various functional groups,and achieves gram-scale synthesis.The reaction is a nucleophilic substitution process without the involvement of free radicals.展开更多
Aqueous zinc-ion batteries(ZIBs)are promising candidates for next-generation energy storage,but the problems related to Zn dendrites and side reactions severely hinder their practical applications.Herein,a self-recogn...Aqueous zinc-ion batteries(ZIBs)are promising candidates for next-generation energy storage,but the problems related to Zn dendrites and side reactions severely hinder their practical applications.Herein,a self-recognition separator based on a Bi-based metal-organic framework(GF@CAU-17)is developed for ion management to achieve highly reversible Zn anodes.The GF@CAU-17 has self-recognition behavior to customize selective Zn^(2+)channels,effectively repelling SO_(4)^(2-)and H_(2)O,but facilitating Zn^(2+)conduction.The inherent properties of CAU-17 result in the repulsion of SO_(4)^(2-)ions while disrupting the hydrogen bond network among free H_(2)O molecules,restraining side reactions and by-products.Simultaneously,the zincophilic characteristic of CAU-17 expedites the desolvation of[Zn(H_(2)O)6]^(2+),leading to a self-expedited Zn^(2+)ion pumping effect that dynamically produces a steady and homogeneous Zn^(2+)ion flux,and thereby alleviates concentration polarization.Consequently,a symmetric cell based on the GF@CAU-17 separator can achieve a long lifespan of 4450 h.Moreover,the constructed Zn//GF@CAU-17//MnO_(2)cell delivers a high specific capacity of 221.8 mAh g^(-1)and 88.0%capacity retention after 2000 cycles.展开更多
We report a robust pillar-layered metal-organic framework,Zn‑tfbdc‑dabco(tfbdc:tetrafluoroterephthal-ate,dabco:1,4-diazabicyclo[2.2.2]octane),featuring the fluorinated pore environment,for the preferential binding of ...We report a robust pillar-layered metal-organic framework,Zn‑tfbdc‑dabco(tfbdc:tetrafluoroterephthal-ate,dabco:1,4-diazabicyclo[2.2.2]octane),featuring the fluorinated pore environment,for the preferential binding of propane over propylene and thus highly inverse selective separation of propane/propylene mixture.The inverse propane-selective performance of Zn‑tfbdc‑dabco for the propane/propylene separation was validated by single-component gas adsorption isotherms,isosteric enthalpy of adsorption calculations,ideal adsorbed solution theory calculations,along with the breakthrough experiment.The customized fluorinated networks served as a propane-trap to form more interactions with the exposed hydrogen atoms of propane,as unveiled by the simulation studies at the molecular level.With the advantage of inverse propane-selective adsorption behavior,high adsorption capacity,good cycling stability,and low isosteric enthalpy of adsorption,Zn‑tfbdc‑dabco can be a promising candidate adsorbent for the challenging propane/propylene separation to realize one-step purification of the target propylene substance.展开更多
The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively red...The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively reduce C=C or C=O bonds while preserving other functional groups within the molecule.This approach serves as a critical strategy for the directional synthesis of high-value molecules.However,achieving such selectivity remains challenging due to the thermodynamic equilibrium and kinetic competition between C=O and C=C bonds inα,β-unsaturated systems.Consequently,constructing precisely targeted catalytic systems is essential to overcome these limitations,offering both fundamental scientific significance and industrial application potential.Metal-organic frameworks(MOFs)and their derivatives have emerged as innovative platforms for designing such systems,owing to their programmable topology,tunable pore microenvironments,spatially controllable active sites,and modifiable electronic structures.This review systematically summarizes the research progress of MOF-based catalysts for selec-tive hydrogenation ofα,β-unsaturated aldehydes/ketones in the last decade,with emphasis on the design strategy,conformational relationship,and catalytic mechanism,aiming to provide new ideas for the design of targeted catalyt-ic systems for the selective hydrogenation ofα,β-unsaturated aldehydes/ketones.展开更多
State-selective single-and double-electron capture processes in collisions of S^(5+)ions with helium at energies ranging from 50.8 keV to 100 keV were investigated using cold target recoil ion momentum spectroscopy(CO...State-selective single-and double-electron capture processes in collisions of S^(5+)ions with helium at energies ranging from 50.8 keV to 100 keV were investigated using cold target recoil ion momentum spectroscopy(COLTRIMS).Q-value spectra and projectile scattering angle distributions were obtained.For single-electron capture,single electron capture into n=3 states of the projectile ion is dominant.As the projectile energy increases,the contribution of single electron capture into n=4 states is observed.Experimental relative cross-sections for single-electron capture into different projectile final states were compared with theoretical predictions based on the molecular orbital close-coupling(MOCC)method.In double-electron capture,two-electron populating into the 3s^(2)3p and 3s3p^(2)states of projectile dominates.The reaction window calculated from the classical molecular Coulombic barrier model can qualitatively explain the experimental results.The scattering angle distribution of the multi-peak structure of the double-electron capture process is observed.The database is openly available in Science Data Bank at https://doi.org/10.57760/sciencedb.j00113.00233.展开更多
Compared with natural enzymes, nanozymes have the advantages of high stability and low cost;however,selectivity and sensitivity are key issues that prevent their further development. In this study, we report a cascade...Compared with natural enzymes, nanozymes have the advantages of high stability and low cost;however,selectivity and sensitivity are key issues that prevent their further development. In this study, we report a cascade nanozymatic system with significantly improved selectivity and sensitivity that combines more substrate-specific reactions and sensitive fiuorescence detection. Taking detection of ascorbic acid(AA)as an example, a cascade catalytic reaction system consisting of oxidase-like N-doped carbon nanocages(NC) and peroxidase-like copper oxide(Cu O) improved the reaction selectivity in transforming the substrate into the target product by more than 1200 times against the interference of uric acid. The cascade catalytic reaction system was also applicable for transfer from open reactors into a spatially confined microfiuidic device, increasing the slope of the calibration curves by approximately 1000-fold with a linear detection range of 2.5 nmol/L to 100 nmol/L and a low limit of detection of 0.77 nmol/L. This work offers a new strategy that achieves significant improvements in selectivity and sensitivity.展开更多
The environment-friendly and efficient selective separation of chalcopyrite and molybdenite poses a challenge in mineral pro-cessing.In this study,gum Arabic(GA)was initially proposed as a novel depressant for the sel...The environment-friendly and efficient selective separation of chalcopyrite and molybdenite poses a challenge in mineral pro-cessing.In this study,gum Arabic(GA)was initially proposed as a novel depressant for the selective separation of molybdenite from chalcopyrite during flotation.Microflotation results indicated that the inhibitory capacity of GA was stronger toward molybdenite than chalcopyrite.At pH 8.0 with 20 mg/L GA addition,the recovery rate of chalcopyrite in the concentrate obtained from mixed mineral flota-tion was 67.49%higher than that of molybdenite.Furthermore,the mechanism of GA was systematically investigated by various surface characterization techniques.Contact angle tests indicated that after GA treatment,the hydrophobicity of the molybdenite surface signifi-cantly decreased,but that of the chalcopyrite surface showed no apparent change.Fourier transform-infrared spectroscopy and X-ray photoelectron spectroscopy revealed a weak interaction force between GA and chalcopyrite.By contrast,GA was primarily adsorbed onto the molybdenite surface through chemical chelation,with possible contributions from hydrogen bonding and hydrophobic interactions.Pre-adsorbed GA could prevent butyl xanthate from being adsorbed onto molybdenite.Scanning electron microscopy–energy-dispersive spectrometry further indicated that GA was primarily adsorbed onto the“face”of molybdenite rather than the“edge.”Therefore,GA could be a promising molybdenite depressant for the flotation separation of Cu–Mo.展开更多
The photocatalytic selective oxidation of biomass-derived 5-hydroxymethylfurfural(HMF)offers a sustainable alternative to thermal catalysis.However,the efficiency of this process is significantly limited by inadequate...The photocatalytic selective oxidation of biomass-derived 5-hydroxymethylfurfural(HMF)offers a sustainable alternative to thermal catalysis.However,the efficiency of this process is significantly limited by inadequate light absorption efficiency and the rapid recombination of photogenerated charge carriers in conventional photocatalysts.Herein,we developed a Co_(3)O_(4)/ZnIn_(2)S_(4)(Co_(3)O_(4)/ZIS)photocatalyst,in which Co_(3)O_(4)functions as a multifunctional cocatalyst.This photocatalyst significantly enhances the chemisorption and activation of HMF molecules through interfacial oxygen-hydroxyl interactions.Additionally,the incorporation of narrow-band gap Co_(3)O_(4)broadens the optical absorption range of the composite photocatalyst.Besides,integrating Co_(3)O_(4)with ZnIn_(2)S_(4)leads to a 5.9-fold increase in charge separation efficiency compared to pristine ZnIn_(2)S_(4).The optimized Co_(3)O_(4)/ZIS-3 photocatalyst(3 wt% Co_(3)O_(4)loading)exhibits exceptional selectivity and yield for 2,5-diformylfuran(DFF)under visible light irradiation,achieving 70.4%DFF selectivity with a 5.4-fold enhancement compared to pristine ZnIn_(2)S_(4).Scavenger experiments and electron spin resonance(ESR)spectroscopy indicate that superoxide radicals(O_(2)^(-))and h^(+)are the main active species driving the photocatalytic oxidation of HMF.Molecular simulations reveal that the activation of HMF and the transformation of the intermediate^(*)MF to^(*)DFF are more favorable over the Co_(3)O_(4)/ZIS composite due to lower activation barriers compared to those over ZnIn_(2)S_(4).Through this work,we aim to design highly efficient and affordable photocatalysts for biomass valorization and contribute valuable insights into the mechanisms of photocatalytic oxidation of HMF.展开更多
The hydroformylation of olefins,known as the"oxo reaction",involves the use of syngas(CO/H_(2))to produce aldehyde with an additional carbon atom.However,side reactions such as the isomerization or hydrogena...The hydroformylation of olefins,known as the"oxo reaction",involves the use of syngas(CO/H_(2))to produce aldehyde with an additional carbon atom.However,side reactions such as the isomerization or hydrogenation of olefins often result in unexpected products and other by-products.Recent efforts in developing efficient ligands represent the most effective approach to addressing these challenges.In this study,we described a Bis-OPNN phosphorus ligand facilitated Rh-catalyzed hydroformylation with a high degree of linear selectivity across various olefins.Under mild conditions,a broad range of olefins were efficiently converted into linear aldehydes with high yields and excellent regioselectivity.The protocol also showed impressive functional group tolerance and was successfully applied to modify drugs and natural products,including the total synthesis of(±)-crispine A.Preliminary mechanistic studies revealed that this Bis-OPNN phosphorus ligand anchoring the rhodium catalyst is crucial for controlling the linear selectivity.展开更多
Bisphenol A(BPA)has threatened ecological safety and human health due to its endocrine disrupting effect and widely diffused in the environment.Peroxymonosulfate(PMS)based on oxidation technology exhibits good potenti...Bisphenol A(BPA)has threatened ecological safety and human health due to its endocrine disrupting effect and widely diffused in the environment.Peroxymonosulfate(PMS)based on oxidation technology exhibits good potential for environmental remediation whereas the highly efficient activator needs to be developed.Herein,the Bi OBr(BOB)was synthesized to efficiently activate PMS to remove 95.6%of BPA within 60 min.The observed rate constant of BPA removal in BOB/PMS system is 0.049 min^(-1),which is 60 and 148 times to that of the BOB and PMS processes separately and 129 times to the compared Bi OCl(BOC)/PMS system,respectively.Comparison experiments and analytic methods demonstrate that BOB with a larger content of oxygen vacancies(Ov)can act as the bridge of electron transfer between Bi^(3+)/Bi^(4+)with PMS to enhance the activation ability for PMS,resulting in the production of abundant reactive oxygen species(O_(2)^(·-)and ^(1)O_(2)).Additionally,the breakdown processes of BPA and the toxicity of its byproducts were uncovered,and the potential for actual water treatment was evaluated to confirm the detoxification,efficiency,stability and practical use of the BOB/PMS system for eliminating BPA.This study may widen the application of traditional semiconductors and develop the cost-effective PMS activation methods for environmental remediation.展开更多
Iron-Vanadium(FeV)catalyst showed a unique catalytic activity for the selective oxidation of methanol to formaldehyde;however,due to its complex compositions,the identification of catalytic active sites still remains ...Iron-Vanadium(FeV)catalyst showed a unique catalytic activity for the selective oxidation of methanol to formaldehyde;however,due to its complex compositions,the identification of catalytic active sites still remains challenging,inhibiting the rational design of excellent FeV-based catalysts.Here,in this work,a series of FeV catalysts with various compositions,including FeVO_(4),isolated VO_(x),low-polymerized V_(n)O_(x),and crystalline V_(2)O_(5) were prepared by controlling the preparation conditions,and were applied to methanol oxidation to formaldehyde reaction.A FeV_(1.1) catalyst,which consisted of FeVO_(4) and low-polymerized V_(n)O_(x) species showed an excellent catalytic performance with a methanol conversion of 92.3%and a formaldehyde selectivity of 90.6%,which was comparable to that of conventional iron-molybdate catalyst.The results of CH_(3)OH-IR,O_(2) pulse and control experiments revealed a crucial synergistic effect between FeVO_(4) and low-polymerized V_(n)O_(x).It enhanced the oxygen supply capacity and suitable binding and adsorption strengths for formaldehyde intermediates,contributing to the high catalytic activity and formaldehyde selectivity.This study not only advances the understanding of FeV structure but also offers valuable guidelines for selective methanol oxidation to formaldehyde.展开更多
Metal oxides as support for constructing precious metal single-atom catalysts hold great promise for a wide range of industrial applications,but achieving a high-loading of thermally stable metal single atoms on such ...Metal oxides as support for constructing precious metal single-atom catalysts hold great promise for a wide range of industrial applications,but achieving a high-loading of thermally stable metal single atoms on such supports has been challenging.Herein,we report an innovative strategy for the fabrication of high-density single-atoms(Rh,Ru,Pd)catalysts on CaAl-layered double hydroxides(CaAl-LDH)via isomorphous substitution.The Rh species have occupied Ca^(2+)vacancies within CaAl-LDH laminate by ion-exchange,facilitating a substantial loading of isolated Rh single-atoms.Such catalysts displayed superior performance in the selective hydrogenation to quinoline,pivotal for liquid organic hydrogen storage,and the universality for the hydrogenation of N-heterocyclic aromatic hydrocarbons was also verified.Combining the experimental results and density functional theory calculations,the pathway of quinoline hydrogenation over Rh1CaAl-LDH was proposed.This synthetic strategy marks a significant advancement in the field of single-atom catalysts,expanding their horizons in green chemical processes.展开更多
As the density of wireless networks increases globally, the vulnerability of overlapped dense wireless communications to interference by hidden nodes and denial-of-service (DoS) attacks is becoming more apparent. Ther...As the density of wireless networks increases globally, the vulnerability of overlapped dense wireless communications to interference by hidden nodes and denial-of-service (DoS) attacks is becoming more apparent. There exists a gap in research on the detection and response to attacks on Medium Access Control (MAC) mechanisms themselves, which would lead to service outages between nodes. Classifying exploitation and deceptive jamming attacks on control mechanisms is particularly challengingdue to their resemblance to normal heavy communication patterns. Accordingly, this paper proposes a machine learning-based selective attack mitigation model that detects DoS attacks on wireless networks by monitoring packet log data. Based on the type of detected attack, it implements effective corresponding mitigation techniques to restore performance to nodes whose availability has been compromised. Experimental results reveal that the accuracy of the proposed model is 14% higher than that of a baseline anomaly detection model. Further, the appropriate mitigation techniques selected by the proposed system based on the attack type improve the average throughput by more than 440% compared to the case without a response.展开更多
The utilization of ethane-selective materials for adsorption-based separation technology presents an energy-efficient alternative to cryogenic distillation for ethylene(C_(2)H_(4))purification from ethane(C_(2)H_(6))....The utilization of ethane-selective materials for adsorption-based separation technology presents an energy-efficient alternative to cryogenic distillation for ethylene(C_(2)H_(4))purification from ethane(C_(2)H_(6)).To study the relations between separation performance and pore environments,we carried out the isoreticular chemistry rule to introduce the-NH_(2)groups into a C_(2)H_(6)-selective MOF[Cu_(1.5)(BTC)(DPU)_(1.5)(H_(2)O)_(1.5)],and successfully improved the adsorption capacity and selectivity for C_(2)H_(6)over C_(2)H_(4).The NH_(2)-functionalized MOF[Cu_(1.5)(NH_(2)-BTC)(DPU)_(1.5)(H_(2)O)_(1.5)]with a relatively narrow pore not only forms appropriate pore restriction but also provides additional binding sites to enhance the adsorption capacity of C_(2)H_(6)relative to C_(2)H_(4).Both gas adsorption and dynamic breakthrough results indicated that the-NH_(2)functionalization significantly enhanced the separation performance of materials for C_(2)H_(6)/C_(2)H_(4)mixtures,allowing the production of C_(2)H_(4)with a purity of over 99.99%and a productivity of up to 30.02 L/kg in one step.Theoretical calculations revealed that the synergistic effect of appropriate pore confinement and NH_(2)-modified functional surfaces imposed stronger interactions on C_(2)H_(6)than C_(2)H_(4).展开更多
The efficient catalytic conversion of fossil-based low-carbon small molecules to oxygen-containing chemicals is an attractive research topic in the fields of energy and chemical engineering.The selective oxidation of ...The efficient catalytic conversion of fossil-based low-carbon small molecules to oxygen-containing chemicals is an attractive research topic in the fields of energy and chemical engineering.The selective oxidation of dimethyl ether(DME),which is derived from fossil resources,represents a promising approach to producing high-concentration formaldehyde with low energy consumption.However,there is still a lack of catalysts achieving satisfactory conversion of DME with high selectivity for formaldehyde under mild conditions.In this work,an efficient iron-molybdate(FeMo)catalyst was developed for the selective oxidation of DME to formaldehyde.The DME conversion of 84% was achieved with a superior formaldehyde selectivity(77%)at 300℃,a performance that is superior to all previously reported results.In an approximately 550 h continuous reaction,the catalyst maintained a conversion of 64% and a formaldehyde selectivity of 79%.Combined X-ray diffraction(XRD),Transmission electron microscope(TEM),Ultraviolet-visible spectroscopy(UV-Vis),Hydrogen temperature-programmed reduction(H_(2)-TPR),Fourier transform infrared(FT-IR)analyses,along with density functional theory(DFT)calculations,demonstrated that the excellent FeMo catalyst was composed of active Fe_(2)(MoO_(4))_(3)and MoO_(3)phases,and there was an interaction between them,which contributed to the efficient DME dissociation and smooth hydrogen spillover,leading to a superior DME conversion.With the support of DME/O_(2)pulse experiments,in-situ Raman,in-situ Dimethyl ether infrared spectroscopy(DME-IR)and DFT calculation results,a Mars-van Krevelen(MvK)reaction mechanism was proposed:DME was dissociated on the interface between Fe_(2)(MoO_(4))_(3)and MoO_(3)phases to form active methoxy species firstly,and it dehydrogenated to give hydrogen species;the generated hydrogen species smoothly spilled over from Fe_(2)(MoO_(4))_(3)to MoO_(3)enhanced by the interaction between Fe_(2)(MoO_(4))_(3)and MoO_(3);then the hydrogen species was consumed by MoO_(3),leading to a reduction of MoO_(3),and finally,the reduced MoO_(3)was re-oxidized by O_(2),returning to the initial state.These findings offer valuable insights not only for the development of efficient FeMo catalysts but also for elucidating the reaction mechanism involved in the oxidation of DME to formaldehyde,contributing to the optimized utilization of DME derived from fossil resources.展开更多
An all-solid-state ion-selective electrode(ISE)for the detection of potassium ions in complex media was developed based on functional peptides with both antibacterial and antifouling properties.While exhibiting unique...An all-solid-state ion-selective electrode(ISE)for the detection of potassium ions in complex media was developed based on functional peptides with both antibacterial and antifouling properties.While exhibiting unique antifouling property,the ISE capitalized on the high surface area of the conductive metalorganic framework(MOF)solid transducer layer to facilitate rapid ion-electron transfer,consequently improving the electrode stability.For a short period,the application of a±1 n A current to the ISE resulted in a slight potential drift of 2.5μV/s,while for a long-term stability test,the ISE maintained a stable Nernstian response slope over 8 days.The antifouling and antibacterial peptide effectively eradicated bacteria from the electrode surface while inhibited the adhesion of bacteria and other biological organisms.Both theoretical calculations and experimental results indicated that the incorporation of peptides in the sensing membrane did not compromise the detection performance of the ISE.The prepared antifouling potassium ion-selective electrode exhibited a Nernstian response range spanning from 1.0×10^(–8)mol/L to 1.0×10–3mol/L,with a detection limit of 2.51 nmol/L.Crucially,the prepared solid-contact ISE maintained excellent antifouling and sensing capabilities in actual seawater and human urine,indicating a promising feasibility of this strategy for constructing ISEs suitable for practical application in complex systems.展开更多
The mainstream silver recovery has problems such as resource waste,weak silver selectivity,and complicated operation.Here,self-propelled magnetic enhanced capture hydrogel(magnetic NbFeB/MXene/GO,MNMGH)was prepared by...The mainstream silver recovery has problems such as resource waste,weak silver selectivity,and complicated operation.Here,self-propelled magnetic enhanced capture hydrogel(magnetic NbFeB/MXene/GO,MNMGH)was prepared by self-crosslinking encapsulation method.MNMGH achieved high selectivity(K_(d)=23.31 mL/g)in the acidic range,and exhibited ultrahigh silver recovery capacity(1604.8 mg/g),which greatly improved by 66%with the assistance of in-situ magnetic field.The recovered silver crystals could be directly physically exfoliated,without acid/base additions.The selective sieving effect of adsorption,MNMGH preferentially adsorbed Ag(I),and then selectively reduced to Ag(0),realizing dual-selective recovery.The in-situ magnetic field enhanced selective adsorption by enhancing mass transfer,reactivity of oxygen-containing functional groups.Furthermore,density function theory simulations demonstrated that the in-situ magnetic field could lower the silver reduction reaction energy barrier to enhance the selective reduction.Three-drive synergy system(reduction drive,adsorption drive and magnetic drive)achieved ultrahigh silver recovery performance.This study pioneered an in-situ magnetic field assisted enhancement strategy for dual-selective(adsorption/reduction)recovery of precious metal silver,which provided new idea for low-carbon recovery of noble metal from industrial waste liquids.展开更多
基金supported by the University Salah Boubnider-Constantine 3 (Algeria).
文摘This research aims to study the bio-adsorption process of two dyes,Cibacron Green H3G(CG-H3G)and Terasil Red(TR),in a single system and to bring them closer to the industrial textile discharge by a binary mixture of two dyes(TR+CG-H3G).The Cockle Shell(CS)was used as a natural bio-adsorbent.The characterizations of CS were investigated by Fourier transform infrared(FTIR),X-ray diffraction(XRD),scanning electron microscopy(SEM),energy-dispersive X-ray spectroscopy(EDX)and Brunauer–Emmett–Teller(BET).The adsorption potential of Cockle Shells was tested in two cases(single and binary system)and determined by:contact time(0–60 min),bio-adsorption dose(3–15 g/L),initial concentration(10–300 mg/L),temperature(22–61°C)and pH solution(2–12).The study of bio-adsorption(equilibrium and kinetics)was conducted at 22°C.The kinetic studies demon-strated that a pseudo-second-order adsorption mechanism had a good correlation coefficient(R2≥0.999).The Langmuir isotherm modeling provided a well-defined description of TR and CG-H3G bio-adsorption on cockle shells,exhibiting maximum capacities of 29.41 and 3.69 mg/g respectively at 22°C.The thermodynamic study shows that the reaction between the TR,CG-H3G dyes molecules and the bio-adsorbent is exothermic,spontaneous in the range of 22–31°C with the aleatory character decrease at the solid-liquid interface.The study of selectivity in single and binary systems has been performed under optimal operating conditions using the industrial textile rejection pH(pH=6.04).CG-H3G dye is found to have a higher selectivity than TR in single(0–60 min)and binary systems with a range of 6–45 min,as shown by the selectivity measurement.It was discovered that CS has the capability to remove both CG-H3G and TR dyes in both simple and binary systems,making it a superior bio-adsorbent.
基金supported by the National Key Research and Development Program of China(No.2019YFC1803501)the National Natural Science Foundation of China(No.52074357)+2 种基金the Natural Science Foundation of Hunan Province,China(No.2022JJ30713)the Vanadium Titanium Union Foundationthe Project of Technology Innovation Center for Comprehensive Utilization of Strategic Mineral Resources,Ministry of Natural Resources,China。
文摘The potential of 2-amino-1-propanol(AP)as a novel depressant in selectively floating ilmenite from titanaugite under weakly acidic conditions was investigated.Micro-flotation results show that AP significantly reduces the recovery of titanaugite while having no evident impact on ilmenite flotation.Subsequent bench-scale flotation tests further confirm a remarkable improvement in separation efficiency upon the introduction of AP.Contact angle and adsorption tests reveal a stronger affinity of AP towards the titanaugite surface in comparison to ilmenite.Zeta potential measurements and X-ray photoelectron spectroscopy(XPS)analyses exhibit favorable adsorption characteristics of AP on titanaugite,resulting from a synergy of electrostatic attraction and chemical interaction.In contrast,electrostatic repulsion hinders any significant interaction between AP and the ilmenite surface.These findings highlight the potential of AP as a highly efficient depressant for ilmenite flotation,paving the way for reduced reliance on sulfuric acid in the industry.
基金supported by the National Major Scientific and Technological Special Project for“Significant New Drugs Development”(No.2018ZX09201018–028)the nuclear energy development projects of China during the 13thFive Year Plan periodthe key research and development project of the Sichuan Provincial Department of Science and Technology(No.18ZDYF1466)。
文摘Radioactive microspheres have demonstrated excellent therapeutic effects and good tolerance in the treatment of unresectable primary and secondary liver malignancies.This is attributed to precise embolization and potent anti-tumor effect.However,certain limitations such as unstable loading,perfusion stasis,heterogeneous distribution,ectopic distribution,and insufficient dosage,restrict their clinical application.Herein,a novel personalized Y-90 carbon microsphere with high uniformity,high specific activity and high availability(^(90)Y-HUACM)is presented.It is synthesized through planar molecular complex adsorption and chemical deposition solidification.^(90)Y-HUACM exhibited controllable size,excellent biocompatibility,outstanding in vitro and in vivo stability.The radiolabeling efficiency of Y-90 exceeded 99%and the leaching rate of Y-90 is far below 0.1%.Furthermore,the excellent anti-tumor effect,nuclide loading stability,anti-reflux characteristics,precise embolization,and biosafety of^(90)Y-HUACM were validated in a rabbit VX2liver tumor model.In summary,this new,high-performance,and customizable radioactive microsphere provides a superior choice for selective internal radiation treatment of advanced liver cancer is expected to be rapidly applied in clinical practice.
文摘Base-catalyzed nucleophilic substitution reactions ofβ-ketonitrile with azodicarboxylates have been developed.A series of disubstituted C—N coupling products were obtained in good to excellent yields under Et_(3)N catalysis.Monosubstitu-tion C—N bond formation reaction catalyzed by K_(2)CO_(3) also gave novel enol-based target products.This method is simple and mild,with good chemoselectivity,excellent substrate compatibility and tolerance for various functional groups,and achieves gram-scale synthesis.The reaction is a nucleophilic substitution process without the involvement of free radicals.
基金supported by the National Natural Science Foundation of China(22272150)the Major Program of Zhejiang Provincial Natural Science Foundation of China(LD22B030002)+2 种基金the Zhejiang Provincial Ten Thousand Talent Program(2021R51009)the Zhejiang Provincial Natural Science of China(LZ23B030001)the Key Science and Technology Project of Jinhua City(2022-1-083,2023-1-093).
文摘Aqueous zinc-ion batteries(ZIBs)are promising candidates for next-generation energy storage,but the problems related to Zn dendrites and side reactions severely hinder their practical applications.Herein,a self-recognition separator based on a Bi-based metal-organic framework(GF@CAU-17)is developed for ion management to achieve highly reversible Zn anodes.The GF@CAU-17 has self-recognition behavior to customize selective Zn^(2+)channels,effectively repelling SO_(4)^(2-)and H_(2)O,but facilitating Zn^(2+)conduction.The inherent properties of CAU-17 result in the repulsion of SO_(4)^(2-)ions while disrupting the hydrogen bond network among free H_(2)O molecules,restraining side reactions and by-products.Simultaneously,the zincophilic characteristic of CAU-17 expedites the desolvation of[Zn(H_(2)O)6]^(2+),leading to a self-expedited Zn^(2+)ion pumping effect that dynamically produces a steady and homogeneous Zn^(2+)ion flux,and thereby alleviates concentration polarization.Consequently,a symmetric cell based on the GF@CAU-17 separator can achieve a long lifespan of 4450 h.Moreover,the constructed Zn//GF@CAU-17//MnO_(2)cell delivers a high specific capacity of 221.8 mAh g^(-1)and 88.0%capacity retention after 2000 cycles.
文摘We report a robust pillar-layered metal-organic framework,Zn‑tfbdc‑dabco(tfbdc:tetrafluoroterephthal-ate,dabco:1,4-diazabicyclo[2.2.2]octane),featuring the fluorinated pore environment,for the preferential binding of propane over propylene and thus highly inverse selective separation of propane/propylene mixture.The inverse propane-selective performance of Zn‑tfbdc‑dabco for the propane/propylene separation was validated by single-component gas adsorption isotherms,isosteric enthalpy of adsorption calculations,ideal adsorbed solution theory calculations,along with the breakthrough experiment.The customized fluorinated networks served as a propane-trap to form more interactions with the exposed hydrogen atoms of propane,as unveiled by the simulation studies at the molecular level.With the advantage of inverse propane-selective adsorption behavior,high adsorption capacity,good cycling stability,and low isosteric enthalpy of adsorption,Zn‑tfbdc‑dabco can be a promising candidate adsorbent for the challenging propane/propylene separation to realize one-step purification of the target propylene substance.
文摘The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively reduce C=C or C=O bonds while preserving other functional groups within the molecule.This approach serves as a critical strategy for the directional synthesis of high-value molecules.However,achieving such selectivity remains challenging due to the thermodynamic equilibrium and kinetic competition between C=O and C=C bonds inα,β-unsaturated systems.Consequently,constructing precisely targeted catalytic systems is essential to overcome these limitations,offering both fundamental scientific significance and industrial application potential.Metal-organic frameworks(MOFs)and their derivatives have emerged as innovative platforms for designing such systems,owing to their programmable topology,tunable pore microenvironments,spatially controllable active sites,and modifiable electronic structures.This review systematically summarizes the research progress of MOF-based catalysts for selec-tive hydrogenation ofα,β-unsaturated aldehydes/ketones in the last decade,with emphasis on the design strategy,conformational relationship,and catalytic mechanism,aiming to provide new ideas for the design of targeted catalyt-ic systems for the selective hydrogenation ofα,β-unsaturated aldehydes/ketones.
基金Project supported by the National Key Research and Development Program of China(Grant No.2022YFA1602500)the National Natural Science Foundation of China(Grant No.11974358)。
文摘State-selective single-and double-electron capture processes in collisions of S^(5+)ions with helium at energies ranging from 50.8 keV to 100 keV were investigated using cold target recoil ion momentum spectroscopy(COLTRIMS).Q-value spectra and projectile scattering angle distributions were obtained.For single-electron capture,single electron capture into n=3 states of the projectile ion is dominant.As the projectile energy increases,the contribution of single electron capture into n=4 states is observed.Experimental relative cross-sections for single-electron capture into different projectile final states were compared with theoretical predictions based on the molecular orbital close-coupling(MOCC)method.In double-electron capture,two-electron populating into the 3s^(2)3p and 3s3p^(2)states of projectile dominates.The reaction window calculated from the classical molecular Coulombic barrier model can qualitatively explain the experimental results.The scattering angle distribution of the multi-peak structure of the double-electron capture process is observed.The database is openly available in Science Data Bank at https://doi.org/10.57760/sciencedb.j00113.00233.
基金supported by the National Natural Science Foundation of China (Nos. 22174014 and 22074015)。
文摘Compared with natural enzymes, nanozymes have the advantages of high stability and low cost;however,selectivity and sensitivity are key issues that prevent their further development. In this study, we report a cascade nanozymatic system with significantly improved selectivity and sensitivity that combines more substrate-specific reactions and sensitive fiuorescence detection. Taking detection of ascorbic acid(AA)as an example, a cascade catalytic reaction system consisting of oxidase-like N-doped carbon nanocages(NC) and peroxidase-like copper oxide(Cu O) improved the reaction selectivity in transforming the substrate into the target product by more than 1200 times against the interference of uric acid. The cascade catalytic reaction system was also applicable for transfer from open reactors into a spatially confined microfiuidic device, increasing the slope of the calibration curves by approximately 1000-fold with a linear detection range of 2.5 nmol/L to 100 nmol/L and a low limit of detection of 0.77 nmol/L. This work offers a new strategy that achieves significant improvements in selectivity and sensitivity.
基金supported by the National Key Research and Development Program of China(Nos.2022YFC2904502 and 2022YFC2904501)the Major Science and Technology Projects in Yunnan Province,China(No.202202AB080012).
文摘The environment-friendly and efficient selective separation of chalcopyrite and molybdenite poses a challenge in mineral pro-cessing.In this study,gum Arabic(GA)was initially proposed as a novel depressant for the selective separation of molybdenite from chalcopyrite during flotation.Microflotation results indicated that the inhibitory capacity of GA was stronger toward molybdenite than chalcopyrite.At pH 8.0 with 20 mg/L GA addition,the recovery rate of chalcopyrite in the concentrate obtained from mixed mineral flota-tion was 67.49%higher than that of molybdenite.Furthermore,the mechanism of GA was systematically investigated by various surface characterization techniques.Contact angle tests indicated that after GA treatment,the hydrophobicity of the molybdenite surface signifi-cantly decreased,but that of the chalcopyrite surface showed no apparent change.Fourier transform-infrared spectroscopy and X-ray photoelectron spectroscopy revealed a weak interaction force between GA and chalcopyrite.By contrast,GA was primarily adsorbed onto the molybdenite surface through chemical chelation,with possible contributions from hydrogen bonding and hydrophobic interactions.Pre-adsorbed GA could prevent butyl xanthate from being adsorbed onto molybdenite.Scanning electron microscopy–energy-dispersive spectrometry further indicated that GA was primarily adsorbed onto the“face”of molybdenite rather than the“edge.”Therefore,GA could be a promising molybdenite depressant for the flotation separation of Cu–Mo.
基金financially supported by the National Key Research and Development Program of China(No.2022YFB3805400)the National Natural Science Foundation of China(No.22178297,No.22478327)+3 种基金the Science and Technology Innovation Program of Hunan Province(No.2024RC9009)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDC04010100)the Provincial Natural Science Foundation of Hunan(No.2024JJ5371)the Scientific Research Fund of Hunan Provincial Education Department(No.24A0107)。
文摘The photocatalytic selective oxidation of biomass-derived 5-hydroxymethylfurfural(HMF)offers a sustainable alternative to thermal catalysis.However,the efficiency of this process is significantly limited by inadequate light absorption efficiency and the rapid recombination of photogenerated charge carriers in conventional photocatalysts.Herein,we developed a Co_(3)O_(4)/ZnIn_(2)S_(4)(Co_(3)O_(4)/ZIS)photocatalyst,in which Co_(3)O_(4)functions as a multifunctional cocatalyst.This photocatalyst significantly enhances the chemisorption and activation of HMF molecules through interfacial oxygen-hydroxyl interactions.Additionally,the incorporation of narrow-band gap Co_(3)O_(4)broadens the optical absorption range of the composite photocatalyst.Besides,integrating Co_(3)O_(4)with ZnIn_(2)S_(4)leads to a 5.9-fold increase in charge separation efficiency compared to pristine ZnIn_(2)S_(4).The optimized Co_(3)O_(4)/ZIS-3 photocatalyst(3 wt% Co_(3)O_(4)loading)exhibits exceptional selectivity and yield for 2,5-diformylfuran(DFF)under visible light irradiation,achieving 70.4%DFF selectivity with a 5.4-fold enhancement compared to pristine ZnIn_(2)S_(4).Scavenger experiments and electron spin resonance(ESR)spectroscopy indicate that superoxide radicals(O_(2)^(-))and h^(+)are the main active species driving the photocatalytic oxidation of HMF.Molecular simulations reveal that the activation of HMF and the transformation of the intermediate^(*)MF to^(*)DFF are more favorable over the Co_(3)O_(4)/ZIS composite due to lower activation barriers compared to those over ZnIn_(2)S_(4).Through this work,we aim to design highly efficient and affordable photocatalysts for biomass valorization and contribute valuable insights into the mechanisms of photocatalytic oxidation of HMF.
基金financial support from the National Key Research and Development Program of China(No.2021YFF0600704).
文摘The hydroformylation of olefins,known as the"oxo reaction",involves the use of syngas(CO/H_(2))to produce aldehyde with an additional carbon atom.However,side reactions such as the isomerization or hydrogenation of olefins often result in unexpected products and other by-products.Recent efforts in developing efficient ligands represent the most effective approach to addressing these challenges.In this study,we described a Bis-OPNN phosphorus ligand facilitated Rh-catalyzed hydroformylation with a high degree of linear selectivity across various olefins.Under mild conditions,a broad range of olefins were efficiently converted into linear aldehydes with high yields and excellent regioselectivity.The protocol also showed impressive functional group tolerance and was successfully applied to modify drugs and natural products,including the total synthesis of(±)-crispine A.Preliminary mechanistic studies revealed that this Bis-OPNN phosphorus ligand anchoring the rhodium catalyst is crucial for controlling the linear selectivity.
基金financially supported by the National Key Research and Development Program of China(No.2022YFC3703103)National Natural Science Foundation of China(Nos.22206053,42277427)the Guangzhou Science and Technology Plan Project(No.2024A04J4058)。
文摘Bisphenol A(BPA)has threatened ecological safety and human health due to its endocrine disrupting effect and widely diffused in the environment.Peroxymonosulfate(PMS)based on oxidation technology exhibits good potential for environmental remediation whereas the highly efficient activator needs to be developed.Herein,the Bi OBr(BOB)was synthesized to efficiently activate PMS to remove 95.6%of BPA within 60 min.The observed rate constant of BPA removal in BOB/PMS system is 0.049 min^(-1),which is 60 and 148 times to that of the BOB and PMS processes separately and 129 times to the compared Bi OCl(BOC)/PMS system,respectively.Comparison experiments and analytic methods demonstrate that BOB with a larger content of oxygen vacancies(Ov)can act as the bridge of electron transfer between Bi^(3+)/Bi^(4+)with PMS to enhance the activation ability for PMS,resulting in the production of abundant reactive oxygen species(O_(2)^(·-)and ^(1)O_(2)).Additionally,the breakdown processes of BPA and the toxicity of its byproducts were uncovered,and the potential for actual water treatment was evaluated to confirm the detoxification,efficiency,stability and practical use of the BOB/PMS system for eliminating BPA.This study may widen the application of traditional semiconductors and develop the cost-effective PMS activation methods for environmental remediation.
文摘Iron-Vanadium(FeV)catalyst showed a unique catalytic activity for the selective oxidation of methanol to formaldehyde;however,due to its complex compositions,the identification of catalytic active sites still remains challenging,inhibiting the rational design of excellent FeV-based catalysts.Here,in this work,a series of FeV catalysts with various compositions,including FeVO_(4),isolated VO_(x),low-polymerized V_(n)O_(x),and crystalline V_(2)O_(5) were prepared by controlling the preparation conditions,and were applied to methanol oxidation to formaldehyde reaction.A FeV_(1.1) catalyst,which consisted of FeVO_(4) and low-polymerized V_(n)O_(x) species showed an excellent catalytic performance with a methanol conversion of 92.3%and a formaldehyde selectivity of 90.6%,which was comparable to that of conventional iron-molybdate catalyst.The results of CH_(3)OH-IR,O_(2) pulse and control experiments revealed a crucial synergistic effect between FeVO_(4) and low-polymerized V_(n)O_(x).It enhanced the oxygen supply capacity and suitable binding and adsorption strengths for formaldehyde intermediates,contributing to the high catalytic activity and formaldehyde selectivity.This study not only advances the understanding of FeV structure but also offers valuable guidelines for selective methanol oxidation to formaldehyde.
文摘Metal oxides as support for constructing precious metal single-atom catalysts hold great promise for a wide range of industrial applications,but achieving a high-loading of thermally stable metal single atoms on such supports has been challenging.Herein,we report an innovative strategy for the fabrication of high-density single-atoms(Rh,Ru,Pd)catalysts on CaAl-layered double hydroxides(CaAl-LDH)via isomorphous substitution.The Rh species have occupied Ca^(2+)vacancies within CaAl-LDH laminate by ion-exchange,facilitating a substantial loading of isolated Rh single-atoms.Such catalysts displayed superior performance in the selective hydrogenation to quinoline,pivotal for liquid organic hydrogen storage,and the universality for the hydrogenation of N-heterocyclic aromatic hydrocarbons was also verified.Combining the experimental results and density functional theory calculations,the pathway of quinoline hydrogenation over Rh1CaAl-LDH was proposed.This synthetic strategy marks a significant advancement in the field of single-atom catalysts,expanding their horizons in green chemical processes.
基金supported by the Ministry of Trade,Industry and Energy(MOTIE)under Training Industrial Security Specialist for High-Tech Industry(RS-2024-00415520)supervised by the Korea Institute for Advancement of Technology(KIAT)the Ministry of Science and ICT(MSIT)under the ICT Challenge and Advanced Network of HRD(ICAN)Program(No.IITP-2022-RS-2022-00156310)supervised by the Institute of Information&Communication Technology Planning&Evaluation(IITP).
文摘As the density of wireless networks increases globally, the vulnerability of overlapped dense wireless communications to interference by hidden nodes and denial-of-service (DoS) attacks is becoming more apparent. There exists a gap in research on the detection and response to attacks on Medium Access Control (MAC) mechanisms themselves, which would lead to service outages between nodes. Classifying exploitation and deceptive jamming attacks on control mechanisms is particularly challengingdue to their resemblance to normal heavy communication patterns. Accordingly, this paper proposes a machine learning-based selective attack mitigation model that detects DoS attacks on wireless networks by monitoring packet log data. Based on the type of detected attack, it implements effective corresponding mitigation techniques to restore performance to nodes whose availability has been compromised. Experimental results reveal that the accuracy of the proposed model is 14% higher than that of a baseline anomaly detection model. Further, the appropriate mitigation techniques selected by the proposed system based on the attack type improve the average throughput by more than 440% compared to the case without a response.
基金supported by National Natural Science Foundation of China(Nos.22371226 and 22371225)Natural Science Basic Research Program of Shaanxi(No.2024JC-JCQN-18).
文摘The utilization of ethane-selective materials for adsorption-based separation technology presents an energy-efficient alternative to cryogenic distillation for ethylene(C_(2)H_(4))purification from ethane(C_(2)H_(6)).To study the relations between separation performance and pore environments,we carried out the isoreticular chemistry rule to introduce the-NH_(2)groups into a C_(2)H_(6)-selective MOF[Cu_(1.5)(BTC)(DPU)_(1.5)(H_(2)O)_(1.5)],and successfully improved the adsorption capacity and selectivity for C_(2)H_(6)over C_(2)H_(4).The NH_(2)-functionalized MOF[Cu_(1.5)(NH_(2)-BTC)(DPU)_(1.5)(H_(2)O)_(1.5)]with a relatively narrow pore not only forms appropriate pore restriction but also provides additional binding sites to enhance the adsorption capacity of C_(2)H_(6)relative to C_(2)H_(4).Both gas adsorption and dynamic breakthrough results indicated that the-NH_(2)functionalization significantly enhanced the separation performance of materials for C_(2)H_(6)/C_(2)H_(4)mixtures,allowing the production of C_(2)H_(4)with a purity of over 99.99%and a productivity of up to 30.02 L/kg in one step.Theoretical calculations revealed that the synergistic effect of appropriate pore confinement and NH_(2)-modified functional surfaces imposed stronger interactions on C_(2)H_(6)than C_(2)H_(4).
基金supported by the National Natural Science Foundation of China(U23A2088,22025206)the Dalian Innovation Support Plan for High Level Talents(2022RG13)+2 种基金DICP(Grant:DICP I202453,DICP I202234)the Fundamental Research Funds for the Central Universities(20720220008)support of the Liaoning Key Laboratory of Biomass Conversion for Energy and Material。
文摘The efficient catalytic conversion of fossil-based low-carbon small molecules to oxygen-containing chemicals is an attractive research topic in the fields of energy and chemical engineering.The selective oxidation of dimethyl ether(DME),which is derived from fossil resources,represents a promising approach to producing high-concentration formaldehyde with low energy consumption.However,there is still a lack of catalysts achieving satisfactory conversion of DME with high selectivity for formaldehyde under mild conditions.In this work,an efficient iron-molybdate(FeMo)catalyst was developed for the selective oxidation of DME to formaldehyde.The DME conversion of 84% was achieved with a superior formaldehyde selectivity(77%)at 300℃,a performance that is superior to all previously reported results.In an approximately 550 h continuous reaction,the catalyst maintained a conversion of 64% and a formaldehyde selectivity of 79%.Combined X-ray diffraction(XRD),Transmission electron microscope(TEM),Ultraviolet-visible spectroscopy(UV-Vis),Hydrogen temperature-programmed reduction(H_(2)-TPR),Fourier transform infrared(FT-IR)analyses,along with density functional theory(DFT)calculations,demonstrated that the excellent FeMo catalyst was composed of active Fe_(2)(MoO_(4))_(3)and MoO_(3)phases,and there was an interaction between them,which contributed to the efficient DME dissociation and smooth hydrogen spillover,leading to a superior DME conversion.With the support of DME/O_(2)pulse experiments,in-situ Raman,in-situ Dimethyl ether infrared spectroscopy(DME-IR)and DFT calculation results,a Mars-van Krevelen(MvK)reaction mechanism was proposed:DME was dissociated on the interface between Fe_(2)(MoO_(4))_(3)and MoO_(3)phases to form active methoxy species firstly,and it dehydrogenated to give hydrogen species;the generated hydrogen species smoothly spilled over from Fe_(2)(MoO_(4))_(3)to MoO_(3)enhanced by the interaction between Fe_(2)(MoO_(4))_(3)and MoO_(3);then the hydrogen species was consumed by MoO_(3),leading to a reduction of MoO_(3),and finally,the reduced MoO_(3)was re-oxidized by O_(2),returning to the initial state.These findings offer valuable insights not only for the development of efficient FeMo catalysts but also for elucidating the reaction mechanism involved in the oxidation of DME to formaldehyde,contributing to the optimized utilization of DME derived from fossil resources.
基金supported by the National Natural Science Foundation of China(Nos.22174082,22374085)the Key Research and Development Program of Shandong Province(No.2021ZDSYS30)Qingdao Postdoctoral Innovation Project Funding(No.QDBSH20220201038)。
文摘An all-solid-state ion-selective electrode(ISE)for the detection of potassium ions in complex media was developed based on functional peptides with both antibacterial and antifouling properties.While exhibiting unique antifouling property,the ISE capitalized on the high surface area of the conductive metalorganic framework(MOF)solid transducer layer to facilitate rapid ion-electron transfer,consequently improving the electrode stability.For a short period,the application of a±1 n A current to the ISE resulted in a slight potential drift of 2.5μV/s,while for a long-term stability test,the ISE maintained a stable Nernstian response slope over 8 days.The antifouling and antibacterial peptide effectively eradicated bacteria from the electrode surface while inhibited the adhesion of bacteria and other biological organisms.Both theoretical calculations and experimental results indicated that the incorporation of peptides in the sensing membrane did not compromise the detection performance of the ISE.The prepared antifouling potassium ion-selective electrode exhibited a Nernstian response range spanning from 1.0×10^(–8)mol/L to 1.0×10–3mol/L,with a detection limit of 2.51 nmol/L.Crucially,the prepared solid-contact ISE maintained excellent antifouling and sensing capabilities in actual seawater and human urine,indicating a promising feasibility of this strategy for constructing ISEs suitable for practical application in complex systems.
基金supported by The National Natural Science Foundation of China(52170087,22276137).
文摘The mainstream silver recovery has problems such as resource waste,weak silver selectivity,and complicated operation.Here,self-propelled magnetic enhanced capture hydrogel(magnetic NbFeB/MXene/GO,MNMGH)was prepared by self-crosslinking encapsulation method.MNMGH achieved high selectivity(K_(d)=23.31 mL/g)in the acidic range,and exhibited ultrahigh silver recovery capacity(1604.8 mg/g),which greatly improved by 66%with the assistance of in-situ magnetic field.The recovered silver crystals could be directly physically exfoliated,without acid/base additions.The selective sieving effect of adsorption,MNMGH preferentially adsorbed Ag(I),and then selectively reduced to Ag(0),realizing dual-selective recovery.The in-situ magnetic field enhanced selective adsorption by enhancing mass transfer,reactivity of oxygen-containing functional groups.Furthermore,density function theory simulations demonstrated that the in-situ magnetic field could lower the silver reduction reaction energy barrier to enhance the selective reduction.Three-drive synergy system(reduction drive,adsorption drive and magnetic drive)achieved ultrahigh silver recovery performance.This study pioneered an in-situ magnetic field assisted enhancement strategy for dual-selective(adsorption/reduction)recovery of precious metal silver,which provided new idea for low-carbon recovery of noble metal from industrial waste liquids.
