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1.
Acc Chem Res ; 2024 Aug 27.
Artigo em Inglês | MEDLINE | ID: mdl-39189337

RESUMO

ConspectusThe conversion of C1 molecules to methyl acetate through the carbonylation of dimethyl ether in mordenite zeolite is an appealing reaction and a crucial step in the industrial coal-to-ethanol process. Mordenite zeolite has large 12-membered-ring (12MR) channels (7.0 × 6.5 Å2) and small 8MR channels (5.7 × 2.6 Å2) connected by a side pocket (4.8 × 3.4 Å2), and this unique pore architecture supplies its high catalytic activity to the key step of carbonylation. However, the reaction mechanism of carbonylation in mordenite zeolite is not thoroughly established in that it is able to explain all experimental phenomena and improve its industrial applications, and the classical potential energy surface exerted by static density function theory calculations cannot reflect the reaction kinetics under realistic conditions because the diffusion kinetics of bulk DME (kinetic dimeter: 4.5 Å) and methyl acetate (MA, kinetic dimeter: 5.5 Å) were not well considered and their restricted diffusion in the narrow side pocket and 8MR channels may greatly alter the integrated kinetics of DME carbonylation in mordenite zeolite. Moreover, the precise illustration of the dynamic behaviors of the ketene intermediate and its derivatives (surface acetate and acylium ion) confined within various voids in mordenite has not been effectively portrayed.Advanced ab initio molecular dynamics (AIMD) simulations with or without the acceleration of enhanced sampling methods provide tremendous opportunities for operando modeling of both reaction and diffusion processes and further identify the geometrical structure and chemical properties of the reactants, intermediates, and products in the different confined voids of mordenite under realistic reaction conditions, which enables high consistency between computations and experiments.In this Account, the carbonylation process in mordenite is comprehensively described by the results of decades of continuous research and newly acquired knowledge from both multiscale simulations and in-(ex-)situ spectroscopic experiments. Three primary steps (DME demethylation to surface methoxy species (SMS), carbon-carbon bond coupling between SMS and CO to acetyl species, and methyl acetate formation by acetyl species and methanol/DME) have been respectively studied with a careful consideration of different molecular factors (reactant distribution, concentration, and attack mode). By utilizing the free-energy surface of diffusion and reaction obtained from AIMD simulations, a comprehensive reaction/diffusion kinetic model was formulated for the first time, illustrating the entire zeolite catalytic process. In this context, a comprehensive and informative analysis of the reaction kinetics of carbonylation in mordenite, including the function of the 12MR channels, 8MR channels, and side pockets in the adsorption, diffusion, and reaction of DME carbonylation, was performed. The different channels of mordenite play different roles in all ordered reaction steps, illustrating a highly organized ultramicroscopic reactor that is encompassed.

2.
Small ; : e2404548, 2024 Aug 02.
Artigo em Inglês | MEDLINE | ID: mdl-39092680

RESUMO

Herein, a variety of 2,6-diaminopyridine (DAP) derived nitrogen-doped hierarchically porous carbon (DAP-NHPC-T) prepared from carbonization-induced structure transformation of DAP-Zn-SiO2-P123 nanocomposites are reported, which are facilely prepared from solvent-free co-assembly of block copolymer templates P123 with pyridine-rich monomer of DAP, Zn(NO3)2 and tetramethoxysilane. In the pyrolysis process, P123 and SiO2 templates promote the formation of mesoporous and supermicroporous structures in the DAP-NHPC-T, while high-temperature volatilization of Zn contributed to generation of micropores. The DAP-NHPC-T possess large BET surface areas (≈956-1126 m2 g-1), hierarchical porosity with micro-supermicro-mesoporous feature and high nitrogen contents (≈10.44-5.99 at%) with tunable density of pyridine-based nitrogen sites (≈5.99-3.32 at%), exhibiting good accessibility and reinforced interaction with SO2. Consequently, the DAP-NHPC-T show high SO2 capacity (14.7 mmol g-1, 25 °C and 1.0 bar) and SO2/CO2/N2 IAST selectivities, extraordinary dynamic breakthrough separation efficiency and cycling stability, far beyond any other reported nitrogen-doped metal-free carbon. As verified by in situ spectroscopy and theoretical calculations, the pyridine-based nitrogen sites of the DAP-NHPC-T boost SO2 adsorption via the unique charge transfer, the adsorption mechanism and reaction model have been finally clarified.

3.
Proc Natl Acad Sci U S A ; 118(21)2021 May 25.
Artigo em Inglês | MEDLINE | ID: mdl-34001593

RESUMO

Diffusion is generally faster at higher temperatures. Here, a counterintuitive behavior is observed in that the movement of long-chain molecules slows as the temperature increases under confinement. This report confirms that this anomalous diffusion is caused by the "thermal resistance effect," in which the diffusion resistance of linear-chain molecules is equivalent to that with branched-chain configurations at high temperature. It then restrains the molecular transportation in the nanoscale channels, as further confirmed by zero length column experiments. This work enriches our understanding of the anomalous diffusion family and provides fundamental insights into the mechanism inside confined systems.

4.
Angew Chem Int Ed Engl ; : e202411264, 2024 Aug 13.
Artigo em Inglês | MEDLINE | ID: mdl-39136438

RESUMO

The surface chemistry of CeO2 is dictated by the well-defined facets, which exert great influence on the supported metal species and the catalytic performance. Here we report Pt1/CeO2 catalysts exhibiting specific structures of Pt-O coordination on different facets by using adequate preparation methods. The simple impregnation method results in Pt-O3 coordination on the predominantly exposed {111} facets, while the photo-deposition method achieves oriented atomic deposition for Pt-O4 coordination into the "nano-pocket" structure of {100} facets at the top. Compared to the impregnated Pt1/CeO2 catalyst showing normal redox properties and low-temperature activity for CO oxidation, the photo-deposited Pt1/CeO2 exhibits uncustomary strong metal-support interaction and extraordinary high-temperature stability. The preparation methods dictate the facet-dependent diversity of Pt-O coordination, resulting in the further activity-selectivity trade-off. By applying specific preparation routes, our work provides an example of disentangling the effects of support facets and coordination environments for nano-catalysts.

5.
J Am Chem Soc ; 145(50): 27471-27479, 2023 Dec 20.
Artigo em Inglês | MEDLINE | ID: mdl-37993784

RESUMO

Understanding chemical bond variations is the soul of chemistry as it is essential for any chemical process. The evolution of hydrogen bonds is one of the most fundamental and emblematic events during proton transfer; however, its experimental visualization remains a formidable challenge because of the transient timescales. Herein, by subtly regulating the proton-donating ability of distinct proton donors (zeolites or tungstophosphoric acid), a series of different hydrogen-bonding configurations were precisely manipulated. Then, an advanced two-dimensional (2D) heteronuclear correlation nuclear magnetic resonance (NMR) spectroscopic technique was utilized to simultaneously monitor the electronic properties of proton donors and acceptors (2-13C-acetone or trimethylphosphine oxide) through chemical shifts. Parabolic 1H-13C NMR relationships combined with single-well and double-well potential energy surfaces derived from theoretical simulations quantitatively identified the hydrogen bond types and allowed the evolution of hydrogen bonds to be visualized in diverse acid-base interaction complexes during proton transfer. Our findings provide a new perspective to reveal the nature and evolution of hydrogen bonds and confirm the superiority of 2D NMR techniques in identifying the subtle distinctions of various hydrogen-bonding configurations.

6.
J Am Chem Soc ; 145(14): 7712-7717, 2023 Apr 12.
Artigo em Inglês | MEDLINE | ID: mdl-36862978

RESUMO

Zeolite molecular sieves with at least eight-membered rings are widely applied in industrial applications, while zeolite crystals with six-membered rings are normally regarded as useless products due to the occupancy of the organic templates and/or inorganic cation in the micropores that could not be removed. Herein, we showed that a novel six-membered ring molecular sieve (ZJM-9) with fully open micropores could be achieved by a reconstruction route. The mixed gas breakthrough experiments such as CH3OH/H2O, CH4/H2O, CO2/H2O, and CO/H2O at 25 °C showed that this molecular sieve was efficient for selective dehydration. Particularly, a lower desorption temperature (95 °C) of ZJM-9 than that (250 °C) of the commercial 3A molecular sieve might offer an opportunity for saving more energy in dehydration processes.

7.
J Am Chem Soc ; 145(31): 17284-17291, 2023 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-37489934

RESUMO

Germanosilicate zeolites with various structures have been extensively synthesized, but the syntheses of corresponding zeolite structures in the absence of germanium species remain a challenge. One such example is an ITR zeolite structure, which is a twin of the ITH zeolite structure. Through the modification of a classic organic template for synthesizing ITH zeolites and thus designing a new organic template with high compatibility to ITR zeolite assisted by theoretical simulation, we, for the first time, show the Ge-free synthesis of an ITR structure including pure silica, aluminosilicate, and borosilicate ITR zeolites. These materials have high crystallinity, corresponding to an ITR content of more than 95%. In the methanol-to-propylene (MTP) reaction, the obtained aluminosilicate ITR zeolite exhibits excellent propylene selectivity and a long lifetime compared with conventional aluminosilicate ZSM-5 zeolite. The strategy for the design of organic templates might offer a new opportunity for rational syntheses of novel zeolites and, thus, the development of highly efficient zeolite catalysts in the future.

8.
Inorg Chem ; 62(28): 11152-11167, 2023 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-37387483

RESUMO

Climate change from anthropogenic carbon dioxide (CO2) emissions poses a severe threat to society. A variety of mitigation strategies currently include some form of CO2 capture. Metal-organic frameworks (MOFs) have shown great promise for carbon capture and storage, but several issues must be solved before feasible widespread adoption is possible. MOFs often exhibit reduced chemical stabilities and CO2 adsorption capacities in the presence of water, which is ubiquitous in nature and many practical settings. A comprehensive understanding of water influence on CO2 adsorption in MOFs is necessary. We have used multinuclear nuclear magnetic resonance (NMR) experiments at temperatures ranging from 173 to 373 K, along with complementary computational techniques, to investigate the co-adsorption of CO2 and water across various loading levels in the ultra-microporous ZnAtzOx MOF. This approach yields detailed information regarding the number of CO2 and water adsorption sites along with their locations, guest dynamics, and host-guest interactions. Guest adsorption and motional models proposed from NMR data are supported by computational results, including visualizations of adsorption locations and the spatial distribution of guests in different loading scenarios. The wide variety and depth of information presented demonstrates how this experimental methodology can be used to investigate humid carbon capture and storage applications in other MOFs.

9.
Chem Soc Rev ; 51(11): 4337-4385, 2022 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-35536126

RESUMO

Acid-catalyzed reactions inside zeolites are one type of broadly applied industrial reactions, where carbocations are the most common intermediates of these reaction processes, including methanol to olefins, alkene/aromatic alkylation, and hydrocarbon cracking/isomerization. The fundamental research on these acid-catalyzed reactions is focused on the stability, evolution, and lifetime of carbocations under the zeolite confinement effect, which greatly affects the efficiency, selectivity and deactivation of zeolite catalysts. Therefore, a profound understanding of the carbocations confined in zeolites is not only beneficial to explain the reaction mechanism but also drive the design of new zeolite catalysts with ideal acidity and cages/channels. In this review, we provide both an in-depth understanding of the stabilization of carbocations by the pore confinement effect and summary of the advanced characterization methods to capture carbocations in zeolites, including UV-vis spectroscopy, solid-state NMR, fluorescence microscopy, IR spectroscopy and Raman spectroscopy. Also, we clarify the relationship between the activity and stability of carbocations in zeolite-catalyzed reactions, and further highlight the role of carbocations in various hydrocarbon conversion reactions inside zeolites with diverse frameworks and varying acidic properties.

10.
J Am Chem Soc ; 144(14): 6270-6277, 2022 Apr 13.
Artigo em Inglês | MEDLINE | ID: mdl-35271271

RESUMO

Zeolite nanosheets with excellent mass transfer are attractive, but their successful syntheses are normally resulted from a huge number of experiments. Here, we show the design of a small organic template for the synthesis of self-pillared pentasil (SPP) zeolite nanosheets from theoretical calculations in interaction energies between organic templates and pentasil zeolite skeletons. As expected, the SPP zeolite nanosheets with the thickness at 10-20 nm have been synthesized successfully. Characterizations show that the SPP zeolite nanosheets with about 90% MFI and 10% MEL structures have good crystallinity, the house-of-card morphology, large surface area, and fully four-coordinated aluminum species. More importantly, methanol-to-propylene tests show that the SPP zeolite nanosheets exhibit much higher propylene selectivity and longer reaction lifetime than conventional ZSM-5 zeolite. These results offer a good opportunity to develop highly efficient zeolite catalysts in the future.

11.
J Am Chem Soc ; 144(31): 14269-14277, 2022 08 10.
Artigo em Inglês | MEDLINE | ID: mdl-35914188

RESUMO

Although the mass production of synthetic plastics has transformed human lives, it has resulted in waste accumulation on the earth. Here, we report a low-temperature conversion of polyethylene into olefins. By mixing the polyethylene feed with rationally designed ZSM-5 zeolite nanosheets at 280 °C in flowing hydrogen as a carrier gas, light hydrocarbons (C1-C7) were produced with a yield of up to 74.6%, where 83.9% of these products were C3-C6 olefins with almost undetectable coke formation. The reaction proceeds in multiple steps, including polyethylene melting, flowing to access the zeolite surface, cracking on the zeolite surface, formation of intermediates to diffuse into the zeolite micropores, and cracking into small molecules in the zeolite micropores. The ZSM-5 zeolite nanosheets kinetically matched the cascade cracking steps on the zeolite external surface and within micropores by boosting the intermediate diffusion. This feature efficiently suppressed the intermediate accumulation on the zeolite surface to minimize coke formation. In addition, we found that hydrogen participation in the cracking process could hinder the formation of polycyclic species within zeolite micropores, which also contributes to the rapid molecule diffusion. The coking-resistant polyethylene upcycling process at a low temperature not only overturns the general viewpoint for facile coke formation in the catalytic cracking over the zeolites but also demonstrates how the polyethylene-based plastics can be upcycled to valuable chemicals. In addition to the model polyethylene, the reaction system worked efficiently for the depolymerization of multiple practically used polyethylene-rich plastics, enabling an industrially and economically viable path for dealing with plastic wastes.


Assuntos
Coque , Zeolitas , Alcenos/química , Humanos , Hidrogênio , Plásticos , Polietileno , Zeolitas/química
12.
Acc Chem Res ; 54(10): 2421-2433, 2021 05 18.
Artigo em Inglês | MEDLINE | ID: mdl-33856775

RESUMO

Acid catalysis in heterogeneous systems such as metal oxides and porous zeolites has been widely involved in various catalytic processes for chemical and petrochemical industries. In acid-catalyzed reactions, the performance (e.g., activity and selectivity) is closely associated with the acidic features of the catalysts, viz., type (Lewis vs Brønsted acidity), distribution (external vs internal surface), strength (strong vs weak), concentration (amount), and spatial interactions of acidic sites. The characterization of local structure and acidic properties of these active sites has important implications for understanding the reaction mechanism and the practical catalytic applications of acidic catalysts. Among diverse acidity characterization approaches, the solid-state nuclear magnetic resonance (SSNMR) technique with suitable probe molecules has been recognized as a reliable and versatile tool. Such a probe-assisted SSNMR approach could provide qualitative (type, distribution, and spatial interactions) and quantitative (strength and concentration) information on each acidic site. This Account aims to integrate our recent important findings in determining the structures and acidic characteristics of some typical metal oxide and zeolite catalysts by using the probe-assisted SSNMR technique, as well as clarifying the continuously evolving process of each discrete acidic site under hydrothermal or chemical treatments even at the molecular level with multiscale theoretical simulations.More specifically, we will describe herein the development and applications of the probe-assisted SSNMR methods, such as trimethylphosphine (TMP) and acetonitrile-d3 (CD3CN) in conjunction with advanced two-dimensional (2D) homo- and heteronuclear correlation spectroscopy, for characterizing the structures and properties of acidic sites in varied solid catalysts. Moreover, relevant information regarding the surface fingerprinting of various facets on crystalline metal oxide nanoparticles and active centers inside porous zeolites, the mapping of relevant spatial interactions, and the verification of structure-activity correlation were investigated as well. Relevant discussions are mainly based on the recent NMR experiments of our collaborating research groups, including (i) determining the acidic characterization with probe-assisted SSNMR approaches, (ii) mapping various active centers (or crystalline facets), and (iii) revealing their influence on catalytic performance of solid acid catalyst systems. It is anticipated that this information may provide more in-depth insights toward our fundamental understanding of solid acid catalysis.

13.
Angew Chem Int Ed Engl ; 61(15): e202116269, 2022 Apr 04.
Artigo em Inglês | MEDLINE | ID: mdl-35179283

RESUMO

The frustrated Lewis pair (FLP) concept in homogeneous catalysis was extended to heterogeneous catalysis via the supramolecular system of FLP between deprotonated zeolite framework oxygens and confined carbocations in methanol-to-olefin (MTO) reactions. In this FLP, the polymethylbenzenium (PMB+ ) functioned as the Lewis acid to accept an electron pair, and the deprotonated framework oxygen site acted as the Lewis base to donate an electron pair. This FLP theoretically demonstrated the ability to undergo H2 heterolysis and alkanes dehydrogenation, and this was further confirmed by gas chromatography-mass spectrometer (GC-MS) catalytic experiments inside FLP-containing chabazite zeolites. All these findings not only bring new recognition to the carbocation chemistry in zeolite cages but also put forward a new reaction pathway as one part of MTO reactions.

14.
Angew Chem Int Ed Engl ; 61(27): e202204500, 2022 Jul 04.
Artigo em Inglês | MEDLINE | ID: mdl-35471635

RESUMO

Zeolites have found tremendous applications in the chemical industry. However, the dynamic nature of their active sites under the flow of adsorbate molecules for adsorption and catalysis is unclear, especially in operando conditions, which could be different from the as-synthesized structures. In the present study, we report a structural transformation of the adsorptive active sites in SAPO-34 zeolite by using acetone as a probe molecule under various temperatures. The combination of solid-state nuclear magnetic resonance, in situ variable-temperature synchrotron X-ray diffraction, and in situ diffuse-reflectance infrared Fourier-transform spectroscopy allow a clear identification and quantification that the chemisorption of acetone can convert the classical Brønsted acid site adsorption mode to an induced Frustrated Lewis Pairs adsorption mode at increasing temperatures. Such facile conversion is also supported by the calculations of ab-initio molecular-dynamics simulations. This work sheds new light on the importance of the dynamic structural alteration of active sites in zeolites with adsorbates at elevated temperatures.

15.
J Am Chem Soc ; 143(31): 12038-12052, 2021 08 11.
Artigo em Inglês | MEDLINE | ID: mdl-34319735

RESUMO

The industrially important methanol-to-hydrocarbons (MTH) reaction is driven and sustained by autocatalysis in a dynamic and complex manner. Hitherto, the entire molecular routes and chemical nature of the autocatalytic network have not been well understood. Herein, with a multitechnique approach and multiscale analysis, we have obtained a full theoretical picture of the domino cascade of autocatalytic reaction network taking place on HZSM-5 zeolite. The autocatalytic reaction is demonstrated to be plausibly initiated by reacting dimethyl ether (DME) with the surface methoxy species (SMS) to generate the initial olefins, as evidenced by combining the kinetic analysis, in situ DRIFT spectroscopy, 2D 13C-13C MAS NMR, electronic states, and projected density of state (PDOS) analysis. This process is operando tracked and visualized at the picosecond time scale by advanced ab initio molecular dynamics (AIMD) simulations. The initial olefins ignite autocatalysis by building the first autocatalytic cycle-olefins-based cycle-followed by the speciation of methylcyclopentenyl (MCP) and aromatic cyclic active species. In doing so, the active sites accomplish the dynamic evolution from proton acid sites to supramolecular active centers that are experimentally identified with an ever-evolving and fluid feature. The olefins-guided and cyclic-species-guided catalytic cycles are interdependently linked to forge a previously unidentified hypercycle, being composed of one "selfish" autocatalytic cycle (i.e., olefins-based cycle with lighter olefins as autocatalysts for catalyzing the formation of olefins) and three cross-catalysis cycles (with olefinic, MCP, and aromatic species as autocatalysts for catalyzing each other's formation). The unraveled dynamic autocatalytic cycles/network would facilitate the catalyst design and process control for MTH technology.

16.
J Am Chem Soc ; 143(23): 8761-8771, 2021 Jun 16.
Artigo em Inglês | MEDLINE | ID: mdl-34076425

RESUMO

There has been a long debate on how and where active sites are created for molecular adsorption and catalysis in zeolites, which underpin many important industrial applications. It is well accepted that Lewis acidic sites (LASs) and basic sites (LBSs) as active sites in pristine zeolites are generally believed to be the extra-framework Al species and residue anion (OH-) species formed at fixed crystallographic positions after their synthesis. However, the dynamic interactions of adsorbates/reactants with pristine zeotype materials to "create" sites during real conditions remain largely unexplored. Herein, direct experimental observation of the establishment of induced active sites in silicoaluminophosphate (SAPO) by an adsorbate is for the first time made, which contradicts the traditional view of the fixed active sites in zeotype materials. Evidence shows that an induced frustrated Lewis pair (FLP, three-coordinated framework Al as LAS and SiO (H) as LBS) can be transiently favored for heterolytic molecular binding/reactions of competitive polar adsorbates due to their ineffective orbital overlap in the rigid framework. High-resolution magic-angle-spinning solid-state NMR, synchrotron X-ray diffraction, neutron powder diffraction, in situ diffuse reflectance infrared Fourier transform spectroscopy, and ab initio molecular dynamics demonstrate the transformation of a typical Brønsted acid site (Al(OH)Si) in SAPO zeolites to new induced FLP structure for hetereolytic binding upon adsorption of a strong polar adsorbate. Our unprecedented finding opens up a new avenue to understanding the dynamic establishment of active sites for adsorption or chemical reactions under molecular bombardment of zeolitic structures.

17.
J Am Chem Soc ; 143(37): 15440-15452, 2021 09 22.
Artigo em Inglês | MEDLINE | ID: mdl-34478267

RESUMO

Neutral ketene is a crucial intermediate during zeolite carbonylation reactions. In this work, the roles of ketene and its derivates (viz., acylium ion and surface acetyl) associated with direct C-C bond coupling during the carbonylation reaction have been theoretically investigated under realistic reaction conditions and further validated by synchrotron radiation X-ray diffraction (SR-XRD) and Fourier transformed infrared (FT-IR) studies. It has been demonstrated that the zeolite confinement effect has significant influence on the formation, stability, and further transformation of ketene. Thus, the evolution and the role of reactive and inhibitive intermediates depend strongly on the framework structure and pore architecture of the zeolite catalysts. Inside side pockets of mordenite (MOR), rapid protonation of ketene occurs to form a metastable acylium ion exclusively, which is favorable toward methyl acetate (MA) and acetic acid (AcOH) formation. By contrast, in 12MR channels of MOR, a relatively longer lifetime was observed for ketene, which tends to accelerate deactivation of zeolite due to coke formation by the dimerization of ketene and further dissociation to diene and alkyne. Thus, we resolve, for the first time, a long-standing debate regarding the genuine role of ketene in zeolite catalysis. It is a paradigm to demonstrate the confinement effect on the formation, fate, and catalytic consequence of the active intermediates in zeolite catalysis.

18.
Angew Chem Int Ed Engl ; 60(9): 4581-4587, 2021 Feb 23.
Artigo em Inglês | MEDLINE | ID: mdl-33274570

RESUMO

Carbonium ions are an important class of reaction intermediates, but their dynamic evolution is difficult to be monitored by in situ techniques under experimental conditions because of their extremely short lifetime. Probably the most famous case is 2-norbornyl cation (2NB+ ): its existing form (classical or non-classical) had been debated for decades, until the concrete proof of non-classical geometry was achieved by X-ray crystallographic characterization at ultra-low temperature (40 K) and super acidic environment. However, we lack the understanding about 2NB+ at ambient conditions. Herein, by taking advantage of the confinement effect and delocalized acidic environment of zeolites, we successfully stabilized 2NB+ and unequivocally confirmed its "non-classical" structure inside the ZSM-5 zeolite by ab initio molecular dynamics simulations and 13 C solid-state nuclear magnetic resonance experiments. It is the first time to in situ observe the non-classical 2NB+ without the super acidic environment at ambient temperature, which provides a new strategy to expand the carbocation chemistry.

19.
Angew Chem Int Ed Engl ; 60(29): 16149-16155, 2021 07 12.
Artigo em Inglês | MEDLINE | ID: mdl-33977664

RESUMO

Dephosphorylation that removes a phosphate group from substrates is an important reaction for living organisms and environmental protection. Although CeO2 has been shown to catalyze this reaction, cerium is low in natural abundance and has a narrow global distribution (>90 % of these reserves are located within six countries). It is thus imperative to find another element/material with high worldwide abundance that can also efficiently extract the phosphate out of agricultural waste for phosphorus recycle. Using para-nitrophenyl phosphate (p-NPP) as a model compound, we demonstrate that TiO2 with a F-modified (001) surface can activate p-NPP dephosphorylation at temperatures as low as 40 °C. By probe-assisted nuclear magnetic resonance (NMR), it was revealed that the strong electron-withdrawing effect of fluorine makes Ti atoms (the active sites) on the (001) surface very acidic. The bidentate adsorption of p-NPP on this surface further promotes its subsequent activation with a barrier ≈20 kJ mol-1 lower than that of the pristine (001) and (101) surfaces, allowing the activation of this reaction near room temperature (from >80 °C).

20.
J Am Chem Soc ; 142(35): 14877-14889, 2020 09 02.
Artigo em Inglês | MEDLINE | ID: mdl-32786791

RESUMO

The spectroscopic study of oxygen, a vital element in materials, physical, and life sciences, is of tremendous fundamental and practical importance. 17O solid-state NMR (SSNMR) spectroscopy has evolved into an ideal site-specific characterization tool, furnishing valuable information on the local geometric and bonding environments about chemically distinct and, in some favorable cases, crystallographically inequivalent oxygen sites. However, 17O is a challenging nucleus to study via SSNMR, as it suffers from low sensitivity and resolution, owing to the quadrupolar interaction and low 17O natural abundance. Herein, we report a significant advance in 17O SSNMR spectroscopy. 17O isotopic enrichment and the use of an ultrahigh 35.2 T magnetic field have unlocked the identification of many inequivalent carboxylate oxygen sites in the as-made and activated phases of the metal-organic framework (MOF) α-Mg3(HCOO)6. The subtle 17O spectral differences between the as-made and activated phases yield detailed information about host-guest interactions, including insight into nonconventional O···H-C hydrogen bonding. Such weak interactions often play key roles in the applications of MOFs, such as gas adsorption and biomedicine, and are usually difficult to study via other characterization routes. The power of performing 17O SSNMR experiments at an ultrahigh magnetic field of 35.2 T for MOF characterization is further demonstrated by examining activation of the MIL-53(Al) MOF. The sensitivity and resolution enhanced at 35.2 T allows partially and fully activated MIL-53(Al) to be unambiguously distinguished and also permits several oxygen environments in the partially activated phase to be tentatively identified. This demonstration of the very high resolution of 17O SSNMR recorded at the highest magnetic field accessible to chemists to date illustrates how a broad variety of scientists can now study oxygen-containing materials and obtain previously inaccessible fine structural information.


Assuntos
Estruturas Metalorgânicas/química , Teoria da Densidade Funcional , Campos Magnéticos , Espectroscopia de Ressonância Magnética , Estrutura Molecular , Isótopos de Oxigênio
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