Structural Evolution of Lanthanum Hydroxides during Long-Term Phosphate Mitigation: Effect of Nanoconfinement

Environmental Science & Technology, Journal Year: 2020, Volume and Issue: 55(1), P. 665 - 676

Published: Dec. 21, 2020

Lanthanum (La)-based materials are effective in removing phosphate (P) from water to prevent eutrophication. Compared their bulky analogues, La(OH)3 nanoparticles exhibit a higher P removal efficiency and more stable ability when spatially confined inside the host. Consequently, understanding of nanoconfinement effects on long-term evolution La–P structures is crucial for practical use sequestration recycle, which, however, still missing. Here, we describe an attempt explore structures, environment, status nanopores D201 resin, compared nonconfined analogue, over adsorption period 25 days both simulated wastewater real bioeffluent. A combinative X-ray diffraction (XRD), cross-polarization nuclear magnetic resonance (CP-NMR), photoelectron spectroscopy (XPS) techniques confirms transition inner-sphere complexation formation LaPO4·xH2O finally LaPO4 samples. Interestingly, rate structural transformation bioeffluent substantially reduced. Nevertheless, conditions, results much faster larger extent transition. Moreover, also facilitates reverse back La(OH)3. Our work provides scientific basis preferable La-based nanocomposites mitigation, immobilization, recycle application.

Language: Английский

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Nanoconfinement engineering for enchanced adsorption of carbon materials, metal–organic frameworks, mesoporous silica, MXenes and porous organic polymers: a review

Environmental Chemistry Letters, Journal Year: 2021, Volume and Issue: 20(1), P. 563 - 595

Published: Nov. 24, 2021

Language: Английский

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From Macro- to Nanoscale: Finite Size Effects on Metal–Organic Framework Switchability

Trends in Chemistry, Journal Year: 2021, Volume and Issue: 3(4), P. 291 - 304

Published: Jan. 24, 2021

Switchable metal–organic frameworks (MOFs) conquer advanced applications in energy storage, sensing, gas separation, catalysis, and biomedicine. They benefit from unique adsorption characteristics responsive behavior leading to anomalously high separation selectivity deliverable storage capacity.Nanostructuring provides an effective means tailor the of switchable MOFs. The characteristic switching pressure depends on critical crystal dimensions.The understanding size effects affecting stimulus-responsive cooperative transformations is its infancy. Thermodynamic kinetic factors govern size-dependent switchability. General models explaining size-related changes responsivity require further methodological development. Advancement computational analytical tools crucial achieve a deeper surface, interfacial, finite effects. standt out for potential catalysis. MOF switchability mechanisms has progressed significantly over past two decades. Nanostructuring essential integration such materials into thin films, hierarchical composites, membranes biological applications. However, downsizing below dimensions causes dramatic dynamic responsiveness towards external stimuli. We discuss most important experimental findings derive general guidelines hypotheses relevance impact Understanding nanostructure thermodynamics implications tailoring porous systems requires interdisciplinary approach, physical characterization techniques, new modeling strategies cover wider range time length scales. MOFs are among systems, with great diverse as air purification, many more [1.Jiao L. et al.Metal–organic frameworks: structures functional applications.Mater. Today. 2019; 27: 43-68Crossref Scopus (117) Google Scholar,2.Yuan S. al.Stable design, synthesis, applications.Adv. Mater. 2018; 30: 1704303Crossref PubMed (667) Scholar]. An outstanding feature, compared other, traditional materials, their ability transform (switch) between different phases well-defined crystalline triggered by stimuli, often guest inclusion [3.Krause al.Chemistry soft crystals–structural dynamics properties.Angew. Chem. Int. Ed. 2020; 59: 15325-15341Crossref (0) Scholar,4.Schneemann A. al.Flexible frameworks.Chem. Soc. Rev. 2014; 43: 6062-6096Crossref latter leads, some cases, improvements or due ultrahigh [5.Li al.Flexible–robust framework efficient removal propyne propylene.J. Am. 2017; 139: 7733-7736Crossref (136) Scholar] capacity [6.Mason J.A. al.Methane flexible intrinsic thermal management.Nature. 2015; 527: 357-361Crossref (491) terms 'flexible MOF', 'soft crystals', 'switchable MOF' used synonymously [7.Horike al.Soft crystals.Nat. 2009; 1: 695Crossref (1544) Scholar,8.Evans J.D. al.Four-dimensional frameworks.Nat. Commun. 11: 2690Crossref (12) aspect indicated term 'switchability' stepwise (first order) character structural transition (bistability). Recently, even multistable have emerged, remarkable recognition [9.Katsoulidis A.P. al.Chemical control structure uptake conformationally mobile material.Nature. 565: 213-217Crossref (70) Scholar,10.Ehrling al.Adaptive response through reversible disorder–disorder transitions.ChemRxiv. (Published online May 19, 2020. https://doi.org/10.26434/chemrxiv.12326165.v1)Google These phase transitions induced stimuli (e.g., temperature, pressure, vapor electromagnetic radiation) associated latent heat transformation, L, governing energetics bulk transition. activation barrier (EA ΔGǂ) governs kinetics windows metastable states. 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Eng. 313: 724-733Crossref (39) 24.Tian al.Role swing-effect ZIF-8.Dalton Trans. 45: 6893-6900Crossref 25.Zhang al.Crystal-size-dependent nanoporous crystals: adsorption-induced ZIF-8.J. Phys. 118: 20727-20733Crossref (68) 26.Miura H. al.Tuning gate-opening particle distribution DUT-8(Ni) micromixer.Dalton 14002-14011Crossref 27.Kavoosi N. al.Tailoring pillared-layer type DUT-8(Ni).Dalton 4685-4695Crossref (35) 28.Ehrling al.Crystal versus paddle wheel deformability: selective gated DUT-8(Co) DUT-8(Ni).J. 7: 21459-21475Crossref 29.Abylgazina pillared layer engineering.CrystEngComm. November 3, https://doi.org/10.1039/D0CE01497D)Google 30.Krause al.The temperature Zr-based DUT-98.Beilstein Nanotechnol. 10: 1737-1744Crossref 31.Krause effect crystallite amplification solids.Nat. 9: 1573Crossref (18) 32.Krause defects negative DUT-49 analyzed situ 129Xe NMR spectroscopy.J. 32: 4641-4650Crossref (3) 33.Wannapaiboon al.Control layered-pillared anchored surfaces.Nat. 346Crossref (9) 34.Haraguchi al.Emergence surface-and interface-induced properties films.Eur. Inorg. 2018: 1697-1706Crossref (10) 35.Omiya al.Nanosheet synthesis sandwich-like reaction field enhanced pressures.ACS Appl. Nano 3779-3784Crossref 36.Saitoh E. al.Reduction polymers built luminescent Ru (II)-metalloligands.Cryst. Growth Des. 16: 7051-7057Crossref (2) 37.Yang X. al.Flexibility tunable micrometer submillimeter scale xylene isomer separation.Research. 2019: 9463719Crossref (6) Hence, crucial. reduced infancy but decisive application platforms 1).Figure 2Prototypical Gas Adsorption Isotherms (Unbroken: Adsorption; Broken: Desorption) Impact Downsizing.Show full captionThe purple lines show isotherm macrosized crystals; orange line result nanoregime. (A) Gating (purple, macro) suppression downscaling I rigid (orange, nano), (B) (C) (NGA) rigidification (D) gate-shift hysteresis widening, (E) emergence.View Large Image Figure ViewerDownload (PPT) emergence. In following sections, we identify key this relate these existing theories transitions. outline relevant comprehensive scenario aspects. From this, deduce future directions simulation studies advance nucleation, interfacial effects, surface layers influencing Nanostructures 1 Box 1). increased outer active mass transport advantageous catalytic [38.Herbst al.Brønsted instead Lewis acidity functionalized MIL-101Cr heterogeneous (nano-MOF) catalysis condensation aldehydes alcohols.Inorg. 53: 7319-7333Crossref (108) 39.Li P. csq-net: significant enhancement degradation nerve agent simulant.Chem. 51: 10925-10928Crossref 40.Li al.Nanosizing enzyme carrier accelerating hydrolysis.ACS Nano. 9174-9182Crossref (115) 41.Majewski M.B. al.Enzyme encapsulation catalysis.CrystEngComm. 19: 4082-4091Crossref 42.Semrau A.L. al.Substantial turnover frequency catalysts combined anchoring.ACS Catal. 3203-3211Crossref Ultrathin offer density centers [43.Zhao M. al.Two-dimensional nanosheets.Small Methods. 1600030Crossref Scholar,44.Tan al.Recent advances ultrathin two-dimensional nanomaterials.Chem. 117: 6225-6331Crossref (2006) Crystals biomedical drug delivery [45.Luzuriaga M.A. al.Enhanced stability MOF-encapsulated vaccines immunogenic vivo.ACS Interfaces. 9740-9746Crossref (31) 46.Wang X.-G. al.Construction flexible-on-rigid hybrid-phase controllable multi-drug 18078-18086Crossref 47.Zhuang al.Optimized metal–organic-framework nanospheres delivery: evaluation small-molecule encapsulation.ACS 2812-2819Crossref (463) implementation nanosized processes timely topic [48.Muldoon P.F. al.Mixed microporous blend nano-sized metal-organic exceptional CO2/N2 performance.ACS Lett. 821-828Crossref 49.Wu al.Nanoporous ZIF-67 embedded microporosity performance.J. Membr. Sci. 548: 309-318Crossref (59) 50.Khdhayyer based MIL-101 PIM-1.Sep. Purif. Technol. 212: 545-554Crossref (15) 51.Tien-Binh al.In-situ cross interface linking PIM-1 UiO-66-NH2 aging control.J. 429-438Crossref (54) 52.Ghalei B. CO2 capture dispersion amine-functionalized nanoparticles.Nat. Energy. 17086Crossref (191) Several groups discussed context electrochemical [53.Xiao micro/nanoscaled direct applications.Chem. 49: 301-331Crossref Scholar,54.Pang COF nanosheets: electrochemistry.Chem. Eur. 26: 6402-6422Crossref (19) batteries[55.Jiang al.Metal-organic nanosheets-guided uniform lithium deposition metallic batteries.Energy Stor. 267-273Crossref Scholar,56.Li al.Ultrathin manganese-based low-cost energy-dense anodes coexistence ligand redox activities.ACS 29829-29838Crossref (50) supercapacitors [57.Choi K.M. al.Supercapacitors nanocrystalline frameworks.ACS 7451-7457Crossref (76) 58.Zheng cobalt-organic storage.Chem. 373: 1319-1328Crossref 59.Wang NiCo-MOF high-performance supercapacitor electrodes.ACS Energy 2063-2071Crossref Excellent reviews summarize recent progress nanomaterials [60.Marshall C.R. al.Size nanocrystals.Chem. 9396-9408Crossref Scholar,61.Cai al.Nano-sized applications.Coord. 417: 213366Crossref (11) Scholar].Box 1Application Platform MOFsDynamic featuring repeatable transformations, attractive research [98.Férey G. Serre three-dimensional hybrid matter: facts, analyses, rules consequences.Chem. 38: 1380-1399Crossref (1226) 99.Bureekaew al.Orbital directing copper zinc paddle-wheel origin flexibility.J. 2012; 22: 10249-10254Crossref (44) 100.Evans al.Origins adsorption.Chem. 873-886Abstract Full Text PDF 101.Sarkisov al.On frameworks.J. 136: 2228-2231Crossref (143) 102.Krause al.A pressure-amplifying material transitions.Nature. 532: 348Crossref 103.Carrington E.J. al.Solvent-switchable continuous-breathing behaviour diamondoid influence CH4 selectivity.Nat. 882Crossref (158) 104.Fairen-Jimenez al.Opening gate: ZIF-8 explored experiments simulations.J. 133: 8900-8902Crossref (639) Energy-efficient investigated academia [105.Du al.New high-and low-temperature ZIF-7: elucidation prediction transitions.J. 137: 13603-13611Crossref (30) industry [106.Adil K. al.Gas/vapour ultra-microporous insights structure/separation relationship.Chem. 3402-3430Crossref Scholar,107.Sholl D.S. Lively R.P. Seven chemical separations change world.Nature. 435-437Crossref (932) majority compounds. receiving increasing attention challenging [108.Yu al.CO2 MOFs: studies.Chem. 9674-9754Crossref (462) 109.Bao al.Potential hydrocarbon mixtures.Energy Environ. 3612-3641Crossref 110.Bobbitt N.S. toxic industrial chemicals warfare agents.Chem. 3357-3385Crossref Switchable-framework compounds react selectively triggering density, permeance, optical absorption, and/or magnetism. renders them sensing [111.Yanai al.Gas detection variations fluorescent molecules polymer.Nat. 787-793Crossref (297) 112.Zhao separation.Adv. 1705189-1705223Crossref (323) 113.Schneemann al.Different pillared-layered center.J. 1667-1676Crossref (43) 114.Freund al.Switchable conductive MOF–nanocarbon coatings threshold architectures.ACS 43782-43789Crossref (26) 115.Freund al.MIL-53 (Al)/carbon CO2-sensing pressure.ACS Sustain. 4012-4018Crossref (14) 116.Dong X.-Y. SCC-MOF molecule identification display.J. 2160-2167Crossref (69) Additional include [117.Das R.K. al.Direct crystallographic observation reactions inside pores polymer.Chem. 6866-6872Crossref (89) Scholar,118.Yuan zirconium bioinspired catalysts.Angew. 55: 10776-10780Crossref (121) Scholar], proton-conductive [119.Yang F. sulfonic acid sites proton conduction.Nat. 877-883Crossref (241) [103.Carrington Scholar,120.Taylor M.K. al.Near-perfect achieved templating Co(bdp).J. 140: 10324-10331Crossref Dynamic Because nanostructured needed it understand effec

Language: Английский

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Hybrid scanning electrochemical cell microscopy-interference reflection microscopy (SECCM-IRM): tracking phase formation on surfaces in small volumes

Faraday Discussions, Journal Year: 2021, Volume and Issue: 233, P. 122 - 148

Published: Oct. 5, 2021

We describe the combination of scanning electrochemical cell microscopy (SECCM) and interference reflection (IRM) to produce a compelling technique for study interfacial processes track SECCM meniscus status in real-time. allows reactions be confined well defined nm-to-μm-sized regions surface, experiments repeated quickly easily at multiple locations. IRM is highly surface-sensitive which reveals happening (very) close substrate with temporal spatial resolution commensurate typical techniques. By using thin transparent conductive layers on glass as substrates, can coupled SECCM, allow real-time situ optical monitoring that occur within it electrode/electrolyte interface. first use assess stability during voltammetry an indium tin oxide (ITO) electrode neutral pH, demonstrating contact area rather stable over large potential window reproducible, varying by only ca. 5% different approaches. At high cathodic potentials, subtle electrowetting detected quantified. also look inside reveal surface changes extreme assigned possible formation nanoparticles. Finally, we examine effect size driving CaCO3 precipitation ITO result electrochemically-generated pH swings. are able number, distribution morphology material spatiotemporal rationalise some observed deposition patterns finite element method modelling reactive-transport. Growth solid phases surfaces from solution important pathway functional materials SECCM-IRM provides means or operando visualisation tracking these improved fidelity. anticipate this will particularly powerful phase processes, especially throughput nature (where each spot separate experiment) creation datasets, exploring wide experimental parameter landscape.

Language: Английский

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Growth Pattern Control and Nanoarchitecture Engineering of Metal–Organic Framework Single Crystals by Confined Space Synthesis

ACS Central Science, Journal Year: 2022, Volume and Issue: 8(6), P. 718 - 728

Published: May 6, 2022

The nanoarchitecture engineering of metal–organic frameworks (MOFs) is a fascinating but intellectually challenging concept that opens up avenues for both tailoring the properties MOFs and expanding their applications. Herein, we report confined growth ZIF-8 single crystals in three-dimensionally ordered (3DO) macroporous polystyrene replica reveal patterns, morphologies, nanoarchitectures can be highly engineered using concentration precursor. Impressively, favorable situ enables successful fabrication 3DO sphere-assembled or single-crystalline sphere arrays when low- high-concentration precursor solution, respectively, used as feedstock. Furthermore, our strategy extended to preparation other MOF crystals, including ZIF-67 HKUST-1, with similar controllable hierarchical nanoarchitectures. With series diameter-tunable spheres, further unravel interesting size–performance relationship Knoevenagle reaction between benzaldehyde malononitrile, wherein smallest spheres show fastest first-order kinetics. This study not only develops general also provides fundamental knowledge mechanism under spaces.

Language: Английский

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Endurance of chalcogenide optical phase change materials: a review

Optical Materials Express, Journal Year: 2022, Volume and Issue: 12(6), P. 2145 - 2145

Published: March 23, 2022

Chalcogenide phase change materials (PCMs) are truly remarkable compounds whose unique switchable optical and electronic properties have fueled an explosion of emerging applications in electronics photonics. Key to any application is the ability PCMs reliably switch between crystalline amorphous states over a large number cycles. While this issue has been extensively studied case memories, current PCM-based photonic devices show limited endurance. This review discusses various parameters that impact crystallization re-amorphization several PCMs, their failure mechanisms, formulate design rules for enhancing cycling durability these compounds.

Language: Английский

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Crystallization and Polymorphism under Nanoconfinement

Crystal Growth & Design, Journal Year: 2024, Volume and Issue: 24(8), P. 3527 - 3558

Published: March 28, 2024

Crystallization outcomes, polymorph stability rankings, and phase transformation pathways can be significantly altered when crystallization is restricted to dimensions below 1 μm. In this review, we discuss the state of art polymorphism in nanoconfinement. A primer presented regarding prevalent theories for nucleation, their implications nucleation confinement, dependence solubility on crystal size. The various methods discovery control polymorphs are reviewed. Polymorphism under nanoconfinement particularly attractive because it advantageous with respect stabilizing desirable amorphous or metastable crystalline forms. Various experimental employing discussed along related characterization. Several critical features nanoconfinement─differences properties confined liquid phases bulk counterparts, thermotropic size, orientation, polymorphism, kinetics─are presented.

Language: Английский

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Unveiling Confinement Engineering for Achieving High‐Performance Rechargeable Batteries

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(25)

Published: March 7, 2024

Abstract The confinement effect, restricting materials within nano/sub‐nano spaces, has emerged as an innovative approach for fundamental research in diverse application fields, including chemical engineering, membrane separation, and catalysis. This principle recently presents fresh perspectives on addressing critical challenges rechargeable batteries. Within spatial confinement, novel microstructures physiochemical properties have been raised to promote the battery performance. Nevertheless, few clear definitions specific reviews are available offer a comprehensive understanding guide utilizing effect review aims fill this gap by primarily summarizing categorization of effects across various scales dimensions systems. Subsequently, strategic design environments is proposed address existing These solutions involve manipulation physicochemical electrolytes, regulation electrochemical activity, stability electrodes, insights into ion transfer mechanisms. Furthermore, provided deepen foundational achieving high‐performance Overall, emphasizes transformative potential tailoring microstructure electrode materials, highlighting their crucial role designing energy storage devices.

Language: Английский

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Efficient Chemo‐Mechanical Actuator Driven by Generation of Prestress via Glycosaminoglycans Accelerating Intrafibrillar Mineralization of Calcium Carbonate

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 24, 2025

Abstract Huge contractile stresses are generated in collagen‐based matrices via the precipitation of various minerals within collagen fibrils. However, how to regulate level prestress intrafibrillar mineralization remains unclear. Here, it is demonstrated that both, polymorph selection and deposition rate mineral, modified by proteoglycans naturally present native The results show a 50% higher rate, possibly due reduction interfacial energy between precursors. While calcite particles nucleate pure collagen, additional presence glycosaminoglycans leads nucleation vaterite both films tendons, resulting stress more than 10 MPa after 72 h tendons. Moreover, generation can be adjusted changing pH values, temperature, concentration mineralizing solution. conversion chemical mechanical endows tendons with an density 90 J kg −1 , twice biological muscle. By controlling release induced demineralization, designed actuator demonstrates excellent actuation performance. observed chemo‐mechanical effect expected inspire design prestress‐reinforced high‐performance composites.

Language: Английский

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Controls on CaCO3 Polymorphism: From Laboratory Precipitation to Biomineralization across Geological Time

Elements, Journal Year: 2025, Volume and Issue: 21(2), P. 92 - 97

Published: April 1, 2025

Calcium carbonate (CaCO3) forms various mineral polymorphs, including calcite, aragonite, and vaterite, each with distinct physicochemical properties. To benefit from these properties, marine organisms have evolved (some) control on the polymorphs which their biomineral structures are built. This is achieved by modulating conditions at calcification sites nature of functional organic macromolecules that can serve as templates for crystallization. Environmental factors, such seawater chemistry ocean acidification, also affect polymorph selection, impacting organisms’ pathways. Across geologic time, mass extinction events influenced evolutionary-scale skeletal mineralogy trends. The organismal controls CaCO3 polymorphism significant implications ecological industrial applications, offering insights into development environmentally friendly materials tailored

Language: Английский

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