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1.
Sci Total Environ ; 806(Pt 4): 150879, 2022 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-34627893

RESUMO

Anaerobic ammonium-oxidizing (anammox) bacteria are iron abundant and depend heavily on iron-binding proteins. The iron demand of anammox bacteria is relatively large. However, it still remains some doubts where these large quantities of available iron come from and how they are regulated in anammox bacteria. Herein, iron-rich nanoparticles in anammoxosomes were detected by synchrotron soft X-ray tomography coupled with scanning transmission X-ray microscopy (STXM). The iron-rich nanoparticles were identified as ferric oxide (α-Fe2O3) mineral cores, and the local atomic structure of iron-rich nanoparticles was obtained by X-ray absorption fine-structure (XAFS) spectra. The bacterioferritin of Q1Q315 and Q1Q5F8 were detected by proteomics analysis. On this basis, the metabolic pathway centered on iron-rich nanoparticles was proposed.

2.
J Am Chem Soc ; 143(45): 18854-18858, 2021 Nov 17.
Artigo em Inglês | MEDLINE | ID: mdl-34730347

RESUMO

Controlling the chemical environments of the active metal atom including both coordination number (CN) and local composition (LC) is vital to achieve active and stable single-atom catalysts (SACs), but remains challenging. Here we synthesized a series of supported Pt1 SACs by depositing Pt atoms onto the pretuned anchoring sites on nitrogen-doped carbon using atomic layer deposition. In hydrogenation of para-chloronitrobenzene, the Pt1 SAC with a higher CN about four but less pyridinic nitrogen (Npyri) content exhibits a remarkably high activity along with superior recyclability compared to those with lower CNs and more Npyri. Theoretical calculations reveal that the four-coordinated Pt1 atoms with about 1 eV lower formation energy are more resistant to agglomerations than the three-coordinated ones. Composition-wise decrease of the Pt-Npyri bond upshifts gradually the Pt-5d center, and minimal one Pt-Npyri bond features a high-lying Pt-5d state that largely facilitates H2 dissociation, boosting hydrogenation activity remarkably.

3.
J Am Chem Soc ; 143(43): 18001-18009, 2021 Nov 03.
Artigo em Inglês | MEDLINE | ID: mdl-34694127

RESUMO

Iridium-based perovskites show promising catalytic activity for oxygen evolution reaction (OER) in acid media, but the iridium mass activity remains low and the active-layer structures have not been identified. Here, we report highly active 1 nm IrOx particles anchored on 9R-BaIrO3 (IrOx/9R-BaIrO3) that are directly synthesized by solution calcination followed by strong acid treatment for the first time. The developed IrOx/9R-BaIrO3 catalyst delivers a high iridium mass activity (168 A gIr-1), about 16 times higher than that of the benchmark acidic OER electrocatalyst IrO2 (10 A gIr-1), and only requires a low overpotential of 230 mV to reach a catalytic current density of 10 mA cm-2geo. Careful scanning transmission electron microscopy, synchrotron radiation-based X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy analyses reveal that, during the electrocatalytic process, the initial 1 nm IrOx nanoparticles/9R-BaIrO3 evolve into amorphous Ir4+OxHy/IrO6 octahedrons and then to amorphous Ir5+Ox/IrO6 octahedrons on the surface. Such high relative content of amorphous Ir5+Ox species derived from trimers of face-sharing IrO6 octahedrons in 9R-BaIrO3 and the enhanced metallic conductivity of the Ir5+Ox/9R-BaIrO3 catalyst are responsible for the excellent acidic OER activity. Our results provide new insights into the surface active-layer structure evolution in perovskite electrocatalysts and demonstrate new approaches for engineering highly active acidic OER nanocatalysts.

4.
ACS Appl Mater Interfaces ; 13(28): 33363-33370, 2021 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-34236162

RESUMO

Two-dimensional (2D) materials with intrinsic magnetic properties are intensively explored due to their potential applications in low-power-consumption electronics and spintronics. To date, only a handful of intrinsic magnetic 2D materials have been reported. Here, we report a realization of intrinsic ferromagnetic behavior in 2D V2C MXene nanosheets through layer mismatch engineering. The V2C MXene nanosheets with a small-angle twisting show a robust intrinsic ferromagnetic response with a saturation magnetic moment of 0.013 emu/g at room temperature. An in-depth study has been performed by X-ray absorption spectroscopy as well as electron paramagnetic resonance (EPR) and photoelectron spectroscopy analyses. It has been revealed that the symmetry-broken interlayer twisting reduced the degeneracy of V 3d states and the van Hove singularity. This led to a redistribution of the density of electronic states near the Fermi level and consequently activated the Stoner ferromagnetism with improved density of itinerant d electrons. This work highlights V2C MXene as a promising intrinsic room-temperature ferromagnetic material with potential applications in spintronics or spin-based electronics.

5.
Nat Nanotechnol ; 16(10): 1141-1149, 2021 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-34312515

RESUMO

Atomically dispersed metal catalysts maximize atom efficiency and display unique catalytic properties compared with regular metal nanoparticles. However, achieving high reactivity while preserving high stability at appreciable loadings remains challenging. Here we solve the challenge by synergizing metal-support interactions and spatial confinement, which enables the fabrication of highly loaded atomic nickel (3.1 wt%) along with dense atomic copper grippers (8.1 wt%) on a graphitic carbon nitride support. For the semi-hydrogenation of acetylene in excess ethylene, the fabricated catalyst shows extraordinary catalytic performance in terms of activity, selectivity and stability-far superior to supported atomic nickel alone in the absence of a synergizing effect. Comprehensive characterization and theoretical calculations reveal that the active nickel site confined in two stable hydroxylated copper grippers dynamically changes by breaking the interfacial nickel-support bonds on reactant adsorption and making these bonds on product desorption. Such a dynamic effect confers high catalytic performance, providing an avenue to rationally design efficient, stable and highly loaded, yet atomically dispersed, catalysts.

6.
Nat Commun ; 12(1): 1854, 2021 Mar 25.
Artigo em Inglês | MEDLINE | ID: mdl-33767164

RESUMO

Graphene is extremely promising for next-generation spintronics applications; however, realizing graphene-based room-temperature magnets remains a great challenge. Here, we demonstrate that robust room-temperature ferromagnetism with TC up to ∼400 K and saturation magnetization of 0.11 emu g-1 (300 K) can be achieved in graphene by embedding isolated Co atoms with the aid of coordinated N atoms. Extensive structural characterizations show that square-planar Co-N4 moieties were formed in the graphene lattices, where atomically dispersed Co atoms provide local magnetic moments. Detailed electronic structure calculations reveal that the hybridization between the d electrons of Co atoms and delocalized pz electrons of N/C atoms enhances the conduction-electron mediated long-range magnetic coupling. This work provides an effective means to induce room-temperature ferromagnetism in graphene and may open possibilities for developing graphene-based spintronics devices.

7.
Angew Chem Int Ed Engl ; 60(13): 7251-7258, 2021 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-33400363

RESUMO

Single-atom-layer catalysts with fully activated basal-atoms will provide a solution to the low loading-density bottleneck of single-atom catalysts. Herein, we activate the majority of the basal sites of monolayer MoS2 , by doping Co ions to induce long-range ferromagnetic order. This strategy, as revealed by in situ synchrotron radiation microscopic infrared spectroscopy and electrochemical measurements, could activate more than 50 % of the originally inert basal-plane S atoms in the ferromagnetic monolayer for the hydrogen evolution reaction (HER). Consequently, on a single monolayer of ferromagnetic MoS2 measured by on-chip micro-cell, a current density of 10 mA cm-2 could be achieved at the overpotential of 137 mV, corresponding to a mass activity of 28, 571 Ag-1 , which is two orders of magnitude higher than the multilayer counterpart. Its exchange current density of 75 µA cm-2 also surpasses most other MoS2 -based catalysts. Experimental results and theoretical calculations show the activation of basal plane S atoms arises from an increase of electronic density around the Fermi level, promoting the H adsorption ability of basal-plane S atoms.

8.
Nanoscale ; 13(4): 2593-2600, 2021 Feb 04.
Artigo em Inglês | MEDLINE | ID: mdl-33480944

RESUMO

Metal-oxide/hydroxide hybrid nanostructures provide an excellent platform to study the interfacial effects on tailoring the catalysis of metal catalysts. Herein, a hybrid nanostructure of Pt@Co(OH)2 supported on SiO2 was synthesized by incipient wetness impregnation of Co(OH)2 with the aid of H2O2 and successive urea-assisted deposition-precipitation of platinum nanoparticles. The Fenton-like reaction between Co2+ and H2O2 during the impregnation process facilitates the formation of active interfacial sites. This hybrid nanostructure exhibits much higher catalytic activity towards CO oxidation than Pt/SiO2 nanoparticles with a similar Pt loading and particle size. In situ diffuse reflectance infrared Fourier transform spectroscopy was used to track the CO adsorption processes and to identify the reaction intermediates during CO oxidation. It shows that the OH species at the Pt-OH-Co interfacial sites could readily react with CO adsorbed on neighboring Pt to yield CO2 by forming *COOH intermediates and oxygen vacancies. Under the CO + O2 oxidation conditions, O2 molecules are activated by the oxygen vacancy and react with the CO molecules adsorbed on Pt to generate CO2, via forming the highly active *OOH intermediates as observed by DRIFTS.

9.
Small ; 16(52): e2005571, 2020 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-33258310

RESUMO

Planar metal clusters possess high metal utilization, distinct electronic properties, and catalytic functions from their 3D counterparts. However, synthesis of these materials is challenging due to much elevated surface free energies. Here it is reported that silica supported planar bilayer Pt-CoOx subnano clusters, consisting of approximately one atomic layer of Pt and one CoOx layer on top, can be achieved by employing strong-electrostatic interactions during impregnation and precisely-controlled CoOx coating using atomic layer deposition. Such bilayer structure is unambiguously confirmed by electron microscopy and in situ X-ray absorption fine spectroscopy which is never reported before. This synthetic approach can be extended to another eight permutations of planar metal-oxide subnano clusters. The resulting bilayer catalysts, owing to unique electronic properties and the abundant metal-oxide interfaces created, exhibit excellent catalytic performances in the reactions of preferential oxidation of CO in H2 and selective hydrogenation of acetylene, by showing much higher selectivity and intrinsic activities at least 8 and 48 times greater than those conventional oxide coated 3D metal clusters/nanoparticles, highlighting the advances of bilayer interfacial structure. These findings open a new avenue to design abundant and highly active metal-oxide interfaces for advanced metal catalysis.

10.
Nanoscale ; 12(5): 3273-3283, 2020 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-31971202

RESUMO

The structures, compositions and chemical states of metal catalysts are prone to dynamic changes in response to reaction conditions. In this work, a combination of in situ X-ray absorption fine structure spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy has been used to monitor the temperature-dependent structural dynamics in bimetallic Pt-Co(OH)2 nanocatalysts during CO oxidation. Alloying with electron-donating Co promotes the catalytic activity of metallic Pt for CO oxidation at low temperature. At elevated temperatures under an oxidation atmosphere, O2 drives the segregation of the Pt-Co alloy into cobalt oxide and platinum metal, with the extent of alloying sharply decreasing from ∼30% at 300 K to 0 at 473 K. Reduction at high temperature could recover the formation of the Pt-Co alloy with the same alloying extent. The observed structural dynamics could be well correlated with the kinetic behavior of the catalysts. This work highlights the importance of tracking the dynamic structural changes of working catalysts for a correct understanding of their catalytic behavior.

11.
ChemSusChem ; 13(5): 929-937, 2020 Mar 09.
Artigo em Inglês | MEDLINE | ID: mdl-31880398

RESUMO

Metal-N-C is a type of attractive electrocatalyst for efficient CO2 reduction to CO. Because of the ambiguity in their atomic structures, the active sites and catalytic mechanisms of the catalysts have remained under debate. Here, the effects of N and C hybrid coordination on the activity of Ni-N-C catalysts were investigated, combining theoretical and experimental methods. The theoretical calculations revealed that N and C hybrid coordination greatly enhanced the capability of single-atom Ni active sites to provide electrons to reactant molecules and strengthens the bonding of Ni to N and C in the Ni-N-C complexes. During the reaction process, the C and N coordination synergistically optimized the reaction energies in the conversion of CO2 to CO. A good agreement between theoretical calculations and electrochemical experiments was achieved based on the newly developed Ni-N-C electrocatalysts. The activity of hybrid-coordination NiN2 C2 was more than double that of single-coordination NiN4 .

12.
Chem Sci ; 10(37): 8685-8693, 2019 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-31803443

RESUMO

Structural transformations between isomers of nanoclusters provide a platform to tune their properties and understand the fundamental science due to their intimate structure-property correlation. Herein, we demonstrate a reversible transformation between the face-centered cubic (FCC) and icosahedral isomers of Pt1Ag28 nanoclusters accomplished in the ligand-exchange processes. Ligand-exchange of 1-adamantanethiolate protected Pt1Ag28 by cyclohexanethiolate could transform the FCC kernel to the icosahedral isomer. Interestingly, the icosahedral Pt1Ag28 could be reversibly transformed to the FCC configuration when the cyclohexanethiolate ligand is replaced again by 1-adamantanethiolate. A combination of UV-vis absorption, mass spectrometry, photo-luminescence and X-ray absorption fine structure unambiguously identifies that the FCC-to-icosahedral structure transformation of Pt1Ag28 involves two distinct stages: (i) ligand-exchange induced outmost motif transformation and (ii) abrupt innermost kernel transformation. As a result of this structural transformation, the emission wavelength of Pt1Ag28 red-shifts from 672 to 720 nm, and the HOMO-LUMO energy gap reduces from 1.86 to 1.74 eV. This work presents the first example of nanocluster isomers with inter-switching configurations, and will provide new insights into manipulating the properties of nanoclusters through controllably tuning their structures.

13.
Nat Commun ; 10(1): 4998, 2019 11 01.
Artigo em Inglês | MEDLINE | ID: mdl-31676812

RESUMO

Hydrogenation of nitriles represents as an atom-economic route to synthesize amines, crucial building blocks in fine chemicals. However, high redox potentials of nitriles render this approach to produce a mixture of amines, imines and low-value hydrogenolysis byproducts in general. Here we show that quasi atomic-dispersion of Pd within the outermost layer of Ni nanoparticles to form a Pd1Ni single-atom surface alloy structure maximizes the Pd utilization and breaks the strong metal-selectivity relations in benzonitrile hydrogenation, by prompting the yield of dibenzylamine drastically from ∼5 to 97% under mild conditions (80 °C; 0.6 MPa), and boosting an activity to about eight and four times higher than Pd and Pt standard catalysts, respectively. More importantly, the undesired carcinogenic toluene by-product is completely prohibited, rendering its practical applications, especially in pharmaceutical industry. Such strategy can be extended to a broad scope of nitriles with high yields of secondary amines under mild conditions.

14.
ACS Appl Mater Interfaces ; 11(49): 45561-45567, 2019 Dec 11.
Artigo em Inglês | MEDLINE | ID: mdl-31713409

RESUMO

Photocatalytic water splitting over layered nanosheet (NS) catalysts has caught a lot of attention for renewable hydrogen fuel production. However, the weak van der Waals interlayer interactions make it a great challenge to realize an effective dissociation of photogenerated excitons and efficient charge transfer across the interior of layered catalysts during the photocatalysis process. Here, we propose an intercalation strategy of high-valence RuIV atoms to render two-dimensional GaS NS photocatalysts with rapid electron-hole dissociation and long photocarrier lifetime in visible-light-driven water splitting. Experimental and theoretical results unravel that the intercalated single-site Ru, confined in interlayer of GaS NSs, with a hexagonal structural configuration of "Ru1-S6", can serve as an electron-trapped high-speed channel toward simultaneously accelerating electron-hole pairs dissociation and promoting photoelectron transportation through the van der Waals interlayer. Consequently, the as-developed Ru-intercalated GaS NSs can give a notable H2 production rate of 340 µmol g-1 h-1 under visible-light irradiation and an apparent yield of 7% at 420 nm, 38 times that of pure GaS NSs. This study opens up a feasible way for a new design of highly active layered photocatalysts toward high-efficiency solar energy conversion.

15.
J Am Chem Soc ; 141(37): 14515-14519, 2019 Sep 18.
Artigo em Inglês | MEDLINE | ID: mdl-31476119

RESUMO

Developing an active and stable metal single-atom catalyst (SAC) is challenging due to the high surface free energy of metal atoms. In this work, we report that tailoring of the 5d state of Pt1 single atoms on Co3O4 through strong electronic metal-support interactions (EMSIs) boosts the activity up to 68-fold higher than those on other supports in dehydrogenation of ammonia borane for room-temperature hydrogen generation. More importantly, this catalyst also exhibits excellent stability against sintering and leaching, in sharp contrast to the rapid deactivation observed on other Pt single-atom and nanoparticle catalysts. Detailed spectroscopic characterization and theoretical calculations revealed that the EMSI tailors the unoccupied 5d state of Pt1 single atoms, which modulates the adsorption of ammonia borane and facilities hydrogen desorption, thus leading to the high activity. Such extraordinary electronic promotion was further demonstrated on Pd1/Co3O4 and in hydrogenation reactions, providing a new promising way to design advanced SACs with high activity and stability.

16.
ACS Appl Mater Interfaces ; 11(34): 31155-31161, 2019 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-31385491

RESUMO

The activation and modulation of the magnetism of MoS2 nanosheets are critical to the development of their application in next-generation spintronics. Here, we report a synergetic strategy to induce and modulate the ferromagnetism of the originally nonmagnetic MoS2 nanosheets. A two-step experimental method was used to simultaneously introduce substitutional V dopants and sulfur vacancy (Vs) in the MoS2 nanosheet host, showing an air-stable and adjustable ferromagnetic response at room temperature. The ferromagnetism could be modulated by varying the content of Vs through Ar plasma irradiation of different periods, with a maximum saturation magnetization of 0.011 emu g-1 reached at the irradiation time of 6 s (s). Experimental characterizations and first-principles calculations suggest that the adjustable magnetization is attributed to the synergetic effect of the substitutional V dopants and Vs in modulating the band structure of MoS2 nanosheets, resulting from the strong hybridization between the V 3d state and the Vs-induced impurity bands. This work suggests that the synergetic effect of substitutional V atoms and Vs is a promising route for tuning the magnetic interactions in two-dimensional nanostructures.

17.
Nat Commun ; 10(1): 1584, 2019 04 05.
Artigo em Inglês | MEDLINE | ID: mdl-30952850

RESUMO

Monolayer chalcogenide semiconductors with both luminescent and ferromagnetic properties are dreamed for simultaneous polarization and detection of the valley degree of freedom in valleytronics. However, a conventional chalcogenide monolayer lacks these coexisting properties due to their mutually exclusive origins. Herein we demonstrate that robust ferromagnetism and photoluminescence (PL) could be achieved in a (Co, Cr)-incorporated single monolayer MoS2, where the ferromagnetic interaction is activated by Co ions, and the nonradiative recombination channels of excitons is cut off by Cr ions. This strategy brings a 90-fold enhancement of saturation magnetization and 35-fold enhancement of PL intensity than the pristine MoS2 monolayer. The main reasons for the coexisting ferromagnetism and PL are the electronic interactions between the impurity bands of atop Cr adatoms and substitutional Co atoms, as well as the increased content of neutral exciton. Our findings could extend the applications of two-dimensional chalcogenides into spintronics, valleytronic and photoelectric devices.

18.
ACS Appl Mater Interfaces ; 11(12): 11498-11506, 2019 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-30830736

RESUMO

One major challenge for the further development of solid oxide fuel cells is obtaining high-performance cathode materials with sufficient stability against reactions with CO2 present in the ambient atmosphere. However, the enhanced stability is often achieved by using material systems exhibiting decreased performance metrics. The phenomena underlying the performance and stability trade-off has not been well understood. This paper uses antimony-doped SrFeO3-δ as a model material to shed light on the relationship between the structure, stability, and performance of perovskite-structured oxides which are commonly used as cathode materials. X-ray absorption revealed that partial substitution of Fe by Sb leads to a series of changes in the local environment of the iron atom, such as a decrease in the iron oxidation state and increase in the oxygen coordination number. Theoretical calculations show that the structural changes are associated with an increase in both the oxygen vacancy formation energy and metal-oxygen bond energy. The area-specific resistance (ASR) of the perovskite oxide increases with Sb doping, indicating a deterioration of the oxygen reduction activity. Exposure of the materials to CO2 leads to depressed oxygen desorption and an increased ASR, which becomes less pronounced at higher Sb doping levels. Origin of the stability-performance trade-off is discussed based on the structural parameters.

19.
Nature ; 565(7741): 631-635, 2019 01.
Artigo em Inglês | MEDLINE | ID: mdl-30700869

RESUMO

Proton-exchange-membrane fuel cells (PEMFCs) are attractive next-generation power sources for use in vehicles and other applications1, with development efforts focusing on improving the catalyst system of the fuel cell. One problem is catalyst poisoning by impurity gases such as carbon monoxide (CO), which typically comprises about one per cent of hydrogen fuel2-4. A possible solution is on-board hydrogen purification, which involves preferential oxidation of CO in hydrogen (PROX)3-7. However, this approach is challenging8-15 because the catalyst needs to be active and selective towards CO oxidation over a broad range of low temperatures so that CO is efficiently removed (to below 50 parts per million) during continuous PEMFC operation (at about 353 kelvin) and, in the case of automotive fuel cells, during frequent cold-start periods. Here we show that atomically dispersed iron hydroxide, selectively deposited on silica-supported platinum (Pt) nanoparticles, enables complete and 100 per cent selective CO removal through the PROX reaction over the broad temperature range of 198 to 380 kelvin. We find that the mass-specific activity of this system is about 30 times higher than that of more conventional catalysts consisting of Pt on iron oxide supports. In situ X-ray absorption fine-structure measurements reveal that most of the iron hydroxide exists as Fe1(OH)x clusters anchored on the Pt nanoparticles, with density functional theory calculations indicating that Fe1(OH)x-Pt single interfacial sites can readily react with CO and facilitate oxygen activation. These findings suggest that in addition to strategies that target oxide-supported precious-metal nanoparticles or isolated metal atoms, the deposition of isolated transition-metal complexes offers new ways of designing highly active metal catalysts.

20.
ACS Appl Mater Interfaces ; 10(37): 31648-31654, 2018 Sep 19.
Artigo em Inglês | MEDLINE | ID: mdl-30156104

RESUMO

Reversible manipulation of the magnetic behavior of two-dimensional van der Waals crystals is crucial for expanding their applications in spin-based information-processing technologies. However, to date, most experimental approaches to tune the magnetic properties are single way and have very limited practical applications. Here, we report an interface charge-transfer method for obtaining a reversible and air-stable magnetic response at room temperature in Mn-doped MoS2 nanosheets. By adsorption of benzyl viologen (BV) molecules as the charge donor, the saturation magnetization of Mn-doped MoS2 nanosheets is enhanced by a magnitude of 60%, and the magnetization can be restored to the original value when the adsorbed BV molecules are removed. This cycle can be repeated many times on the same sample without detectable degradation. Experimental characterizations and first-principles calculations suggest that the enhanced magnetization can be attributed to the increase of Mn magnetic moment because of the enriched electrons transferred from BV molecules. This work shows that interface charge transfer may open up a new pathway for reversibly tuning the exchange interactions in two-dimensional nanostructures.

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