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1.
Nanoscale ; 13(45): 19247-19254, 2021 Nov 25.
Artigo em Inglês | MEDLINE | ID: mdl-34787144

RESUMO

Two-dimensional (2D) metal-organic frameworks (MOFs) serve as emerging electrocatalysts due to their high conductivity, chemical tunability, and accessibility of active sites. We herein proposed a series of 2D MOFs with different metal atoms and organic linkers with the formula M3C12X12 (M = Cr, Mo, and W; X = NH, O, S, and Se) to design efficient nitrogen reduction reaction (NRR) electrocatalysts. Our theoretical calculations showed that metal atoms in M3C12X12 can efficiently capture and activate N2 molecules. Among these candidates, W3C12X12 (X = O, S, and Se) show the best NRR performance due to their high activity and selectivity as well as low limiting potential (-0.59 V, -0.14 V, and -0.01 V, respectively). Moreover, we proposed a d-band center descriptor strategy to screen out the high activity and selectivity of M3C12X12 for the NRR. Therefore, our work not only demonstrates a class of promising electrocatalysts for the NRR but also provides a strategy for further predicting the catalytic activity of 2D MOFs.

2.
Inorg Chem ; 2021 Nov 17.
Artigo em Inglês | MEDLINE | ID: mdl-34787407

RESUMO

Critically, the central metal atoms along with their coordination environment play a significant role in the catalytic performance of single-atom catalysts (SACs). Herein, 12 single Fe, Mo, and Ru atoms supported on defective graphene are theoretically deigned for investigation of their structural and electronic properties and catalytic nitrogen reduction reaction (NRR) performance using first-principles calculations. Our results reveal that graphene with vacancies can be an ideal anchoring site for stabilizing isolated metal atoms owing to the strong metal-support interaction, forming stable TMCx or TMNx active centers (x = 3 or 4). Six SACs are screened as promising NRR catalyst candidates with excellent activity and selectivity during NRR, and RuN3 is identified as the optimal one with an overpotential of ≥0.10 V via the distal mechanism.

3.
Nat Commun ; 12(1): 6051, 2021 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-34663812

RESUMO

The use of highly-active and robust catalysts is crucial for producing green hydrogen by water electrolysis as we strive to achieve global carbon neutrality. Noble metals like platinum are currently used catalysts in industry for the hydrogen evolution, but suffer from scarcity, high price and unsatisfied performance and stability at large current density, restrict their large-scale implementations. Here we report the synthesis of a type of monolith catalyst consisting of a metal disulfide (e.g., tantalum sulfides) vertically bonded to a conductive substrate of the same metal tantalum by strong covalent bonds. These features give the monolith catalyst a mechanically-robust and electrically near-zero-resistance interface, leading to an excellent hydrogen evolution performance including rapid charge transfer and excellent durability, together with a low overpotential of 398 mV to achieve a current density of 2,000 mA cm-2 as required by industry. The monolith catalyst has a negligible performance decay after 200 h operation at large current densities. In light of its robust and metallic interface and the various choices of metals giving the same structure, such monolith materials would have broad uses besides catalysis.

4.
Nanoscale ; 13(35): 14935-14944, 2021 Sep 17.
Artigo em Inglês | MEDLINE | ID: mdl-34533164

RESUMO

Photocatalytic nitrogen reduction reaction (NRR) is a promising, green route to chemically reducing N2 into NH3 under ambient conditions, correlating to the N2 fixation process of nitrogenase enzymes. To achieve high-yield NRR with sunlight as the driving force, high-performance photocatalysts are essential. One-dimensional silicon nanowires (1D SiNWs) are a great photoelectric candidate, but inactive for NRR due to their inability to capture N2. In this study, we proposed SiNWs doped by p-block elements (B, C, P) to tune the affinity to N2 and demonstrated that two-coordinated boron (B2C) offers an ultra-low overpotential (η) of 0.34 V to catalyze full NRR, which is even much lower than that of flat benchmark Ru(0001) catalysts (η = 0.92 V). Moreover, aspects including suppressed hydrogen evolution reaction (HER), high-spin ground state of the B2C site, and decreased band gap after B-doping ensure the high selectivity and photocatalytic activity. Finally, this work not only shows the potential use of metal-free p-block element-based catalysts, but also would facilitate the development of 1D nanomaterials towards efficient reduction of N2 into NH3.

5.
ACS Nano ; 15(1): 1240-1249, 2021 01 26.
Artigo em Inglês | MEDLINE | ID: mdl-33332960

RESUMO

Construction of nanofluidic devices with an ultimate ion selectivity analogue to biological ion channels has been of great interest for their versatile applications in energy harvesting and conversion, mineral extraction, and ion separation. Herein, we report a three-dimensional (3D) sub-1 nm nanofluidic device to achieve high monovalent metal ion selectivity and conductivity. The 3D nanofluidic channel is constructed by assembly of a carboxyl-functionalized metal-organic framework (MOF, UiO-66-COOH) crystals with subnanometer pores into an ethanediamine-functionalized polymer nanochannel via a nanoconfined interfacial growth method. The 3D UiO-66-COOH nanofluidic channel achieves an ultrahigh K+/Mg2+ selectivity up to 1554.9, and the corresponding K+ conductivity is one to three orders of magnitude higher than that in bulk. Drift-diffusion experiments of the nanofluidic channel further reveal an ultrahigh charge selectivity (K+/Cl-) up to 112.1, as verified by the high K/Cl content ratio in UiO-66-COOH. The high metal ion selectivity is attributed to the size-exclusion, charge selectivity, and ion binding of the negatively charged MOF channels. This work will inspire the design of diverse MOF-based nanofluidic devices for ultimate ion separation and energy conversion.

6.
Inorg Chem ; 59(23): 17631-17637, 2020 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-33179923

RESUMO

Fluorination is an effective way of tuning the physicochemical property and activity of TiO2 nanocrystallites, which usually requires a considerable amount of hydrofluoric acid (or NH4F) for a typical F/Ti molar ratio, RF, of 0.5-69.0 during synthesis. This has consequential environmental issues due to the high toxicity and hazard of the reactants. In the present work, an environmentally benign fluorination approach is demonstrated that uses only a trace amount of sodium fluoride with an RF of 10-6 during synthesis. While it maintained the desirable high surface area (102.4 m2/g), the trace-level fluorination enabled significant enhancements on photocatalytic activities (e.g., a 56% increase on hydrogen evolution rate) and heavy metal Pb(II) removal (31%) of the mesoporous TiO2. This can be attributed to enriched Ti3+ and localized spatial charge separation due to fluorination as proved by X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance spectroscopy (EPR), and density functional theory (DFT) analyses.

7.
Phys Chem Chem Phys ; 22(38): 21761-21767, 2020 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-32959820

RESUMO

It is challenging to identify effective electrocatalysts for nitrogen reduction in order to advance electrochemical nitrogen fixation under ambient conditions using methods that are powered by renewable energy. Silicon carbide was investigated computationally as a metal-free, surface-derived catalyst for the electrocatalytic nitrogen reduction reaction. As demonstrated by first-principle calculations, Si-terminated and C-terminated surfaces, with the Si and C as active sites, are all reactive for dinitrogen capture and activation, resembling the catalytic behavior of popular B-based electrocatalysts, but the latter (C-terminated) offers an ultralow over-potential of 0.39 V, which is lower than most metals and alloys, while retarding hydrogen evolution. This research enriches the design of catalysts for dinitrogen fixation under ambient conditions, and also highlights a new direction for Si-based materials for nitrogen reduction.

8.
Adv Mater ; 32(40): e2004382, 2020 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-32876982

RESUMO

Electrochemical nitrogen reduction reaction (NRR) over nonprecious-metal and single-atom catalysts has received increasing attention as a sustainable strategy to synthesize ammonia. However, the atomic-scale regulation of such active sites for NRR catalysis remains challenging because of the large distance between them, which significantly weakens their cooperation. Herein, the utilization of regular surface cavities with unique microenvironment on graphitic carbon nitride as "subnano reactors" to precisely confine multiple Fe and Cu atoms for NRR electrocatalysis is reported. The synergy of Fe and Cu atoms in such confined subnano space provides significantly enhanced NRR performance, with nearly doubles ammonia yield and 54%-increased Faradic efficiency up to 34%, comparing with the single-metal counterparts. First principle simulation reveals this synergistic effect originates from the unique Fe-Cu coordination, which effectively modifies the N2 absorption, improves electron transfer, and offers extra redox couples for NRR. This work thus provides new strategies of manipulating catalysts active centers at the sub-nanometer scale.

9.
Nanoscale ; 12(29): 15880-15887, 2020 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-32697243

RESUMO

In this study, using the density functional theory calculations, we present a strategy to improve the activity and selectivity of electrocatalytic CO reduction reactions (CORRs) towards CH4 production occurring on single transition metal (TM) atoms embedded in a defective MXene Mo2-xTiC2Oy with one oxygen vacancy. Owing to the unique geometric and electronic structures, the exposed TM-Mo-Mo triangle can serve as an active site, and the surrounding oxygen atoms can break the scaling relationships between the CORR intermediates via the steric hindrance. The synergistic effects result in an excellent catalytic performance for CORRs. Based on the extensive investigation of series of candidates, W-decorated MXene was identified as the most promising CORR electrocatalyst, with a high selective activity towards the CH4 production and strong suppression of competing hydrogen evolution reactions (HERs). The adsorption free energy of *COH [ΔGads (*COH)] is proposed as a descriptor to establish a relationship with the catalytic activity. Our rational design principles and rapid screening methods may shed light on the development of other highly efficient CORR electrocatalysts, as well as the other electrochemical systems.

10.
ACS Appl Mater Interfaces ; 12(22): 24845-24854, 2020 Jun 03.
Artigo em Inglês | MEDLINE | ID: mdl-32374583

RESUMO

In this work, we prepared flexible carbon-fiber/semimetal Bi nanosheet arrays from solvothermal-synthesized carbon-fiber/Bi2O2CO3 nanosheet arrays via a reductive calcination process. The flexible carbon-fiber/semimetal Bi nanosheet arrays can function as photocatalysts and photoelectrocatalysts for 2,4-dinitorphenol oxidation. Compared with carbon-fiber/Bi2O2CO3 nanosheet arrays, the newly designed flexible carbon-fiber/semimetal Bi nanosheet arrays show enhanced ultraviolet-visible (UV-vis) light absorption efficiency and photocurrent, photocatalytic, and photoelectrocatalytic activities. Photocatalytic analyses indicate that the surface plasmon resonance (SPR) of semimetal Bi occurs under solar-simulated light irradiation during the photocatalytic process. The carbon-fiber traps the hot electrons exerted from the SPR of semimetal Bi and creates holes in the semimetal Bi nanosheets, which boosts the photocatalytic activity of the carbon fiber through plasmonic sensitization. Both photocatalytic experiments and density functional theory (DFT) calculations indicate that the electrons transferred to the carbon fiber and the holes created in semimetal Bi contribute to the formation of •O2- and •OH, respectively. The synergistic effect between electrocatalysis and photocatalysis under the solar-simulated light results in almost complete degradation of 2,4-dinitorphenol during the photoelectrocatalytic process. This work realizes a non-noble-metal plasmonic catalyst and provides a new avenue for the commercialization of photocatalysis and photoelectrocatalysis using the separable and recyclable carbon-fiber/semimetal Bi nanosheet arrays in the environment-related field.

11.
Nanoscale ; 12(16): 8775-8784, 2020 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-32270841

RESUMO

The face-to-face contact of a vertical heterojunction is beneficial to charge interaction in photocatalysis. However, constructing a vertical heterojunction with uncompromised redox ability still remains a challenge. Herein, we report the successful synthesis of a WO3-TiO2 vertical heterojunction via establishing an internal electric field across the interface. Experimental investigation and computational simulations reveal that strong electric coupling occurs at the WO3-TiO2 interface forming an internal electric field. The internal electric field induces a Z-scheme charge-carrier transfer through the heterojunction under light irradiation, which leads to effective charge separation and maintains high reaction potentials of charge-carriers. The improved photocatalytic activity of the WO3-TiO2 heterojunction is proved by enhanced generation of reactive oxygen species and accelerated Escherichia coli (E. coli) disinfection. This study provides new insights into understanding and designing Z-scheme heterogeneous photocatalysts.

12.
Nat Mater ; 19(7): 767-774, 2020 07.
Artigo em Inglês | MEDLINE | ID: mdl-32152561

RESUMO

Biological ion channels have remarkable ion selectivity, permeability and rectification properties, but it is challenging to develop artificial analogues. Here, we report a metal-organic framework-based subnanochannel (MOFSNC) with heterogeneous structure and surface chemistry to achieve these properties. The asymmetrically structured MOFSNC can rapidly conduct K+, Na+ and Li+ in the subnanometre-to-nanometre channel direction, with conductivities up to three orders of magnitude higher than those of Ca2+ and Mg2+, equivalent to a mono/divalent ion selectivity of 103. Moreover, by varying the pH from 3 to 8 the ion selectivity can be tuned further by a factor of 102 to 104. Theoretical simulations indicate that ion-carboxyl interactions substantially reduce the energy barrier for monovalent cations to pass through the MOFSNC, and thus lead to ultrahigh ion selectivity. These findings suggest ways to develop ion selective devices for efficient ion separation, energy reservation and power generation.


Assuntos
Estruturas Metalorgânicas , Metais/química , Nanoestruturas/química , Cátions Monovalentes , Condutividade Elétrica , Humanos
13.
ChemSusChem ; 13(2): 328-333, 2020 Jan 19.
Artigo em Inglês | MEDLINE | ID: mdl-31777179

RESUMO

Photoinduced charge carrier behavior is critical in determining photoelectrocatalytic activity. In this study, a unique layer-doped metal-free polymeric carbon nitride (C3 N4 ) photoanode is fabricated by using one-pot thermal vapor deposition. With this method, a photoanode consisting of a phosphorus-doped top layer, boron-doped middle layer, and pristine C3 N4 bottom layer, was formed as a result of the difference in thermal polymerization kinetics associated with the boron-containing H3 BO3 -melamine complex and the phosphorus-containing H3 PO4 -dicyandiamide complex. This layer-doping fabrication strategy effectively contributes to the formation of dual junctions that optimizing charge carrier behavior. The ternary-layer C3 N4 photoanode exhibits significantly enhanced photoelectrochemical water oxidation activity compared to pristine C3 N4 , with a record photocurrent density of 150±10 µA cm-2 at 1.23 V vs. RHE. This layer-doping strategy provides an effective means for design and fabrication of photoelectrodes for solar water oxidation.

14.
Chem Sci ; 11(16): 4119-4124, 2020 Mar 23.
Artigo em Inglês | MEDLINE | ID: mdl-34122877

RESUMO

Reactivity trends on transition metals can generally be understood through the d-band model, but no analogous theory exists for transition metal oxides. This limits the generality of analyses in oxide-based catalysis and surface chemistry and has motivated the appearance of numerous descriptors. Here we show that oxygen vacancy formation energy (ΔE Vac) is an inexpensive yet accurate and general descriptor for trends in transition-state energies, which are usually difficult to assess. For rutile-type oxides (MO2 with M = 3d metals from Ti to Ni), we show that ΔE Vac captures the trends in C-O and N-O bond scission of CO2, CH3OH, N2O, and NH2OH at oxygen vacancies. The proportionality between ΔE Vac and transition-state energies is rationalized by analyzing the oxygen-metal bonds, which change from ionic to covalent from TiO2 to NiO2. ΔE Vac may be used to design oxide catalysts, in particular those where lattice oxygen and/or oxygen vacancies participate in the catalytic cycles.

15.
Angew Chem Int Ed Engl ; 58(46): 16644-16650, 2019 Nov 11.
Artigo em Inglês | MEDLINE | ID: mdl-31497911

RESUMO

As a metal-free nitrogen reduction reaction (NRR) photocatalyst, g-C3 N4 is available from a scalable synthesis at low cost. Importantly, it can be readily functionalized to enhance photocatalytic activities. However, the use of g-C3 N4 -based photocatalysts for the NRR has been questioned because of the elusive mechanism and the involvement of N defects. This work reports the synthesis of a g-C3 N4 photocatalyst modified with cyano groups and intercalated K+ (mCNN), possessing extended visible-light harvesting capacity and superior photocatalytic NRR activity (NH3 yield: 3.42 mmol g-1 h-1 ). Experimental and theoretical studies suggest that the -C≡N in mCNN can be regenerated through a pathway analogous to Mars van Krevelen process with the aid of the intercalated K+ . The results confirm that the regeneration of the cyano group not only enhances photocatalytic activity and sustains the catalytic cycle, but also stabilizes the photocatalyst.

16.
ACS Nano ; 13(10): 11874-11881, 2019 Oct 22.
Artigo em Inglês | MEDLINE | ID: mdl-31525951

RESUMO

Metallic transition metal dichalcogenides, such as tantalum disulfide (TaS2), have recently emerged as promising electrocatalysts for the hydrogen evolution reaction. This work reports an effective strategy to further tune their performance through interfacial engineering, including lattice mismatch and electron injection between electrocatalysts and the underlying substrates. A unique two-zone chemical vapor deposition technique has been developed, and 2D TaS2 has been successfully grown on four different substrates, including glassy carbon, carbon fibers, Mo foil, and Au foil, providing excellent platforms to study catalyst-substrate interactions. Among them, TaS2 on Au foil offers the best performance with lowest overpotential and smallest charge transfer resistance, due to a suitable lattice mismatch and charge injection between TaS2 and Au, as revealed by theoretical calculations and experimental measurements. This work highlights the key roles the substrate plays in the catalysis and demonstrates the validity of interfacial engineering in catalyst design.

17.
Nat Commun ; 10(1): 3483, 2019 Aug 02.
Artigo em Inglês | MEDLINE | ID: mdl-31375663

RESUMO

The growing demand for advanced lithium-ion batteries calls for the continued development of high-performance positive electrode materials. Polyoxyanion compounds are receiving considerable interest as alternative cathodes to conventional oxides due to their advantages in cost, safety and environmental friendliness. However, polyanionic cathodes reported so far rely heavily upon transition-metal redox reactions for lithium transfer. Here we show a polyanionic insertion material, Li2Fe(C2O4)2, in which in addition to iron redox activity, the oxalate group itself also shows redox behavior enabling reversible charge/discharge and high capacity without gas evolution. The current study gives oxalate a role as a family of cathode materials and suggests a direction for the identification and design of electrode materials with polyanionic frameworks.

18.
Front Chem ; 7: 468, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31334217

RESUMO

Herein, we present a systematic study on the preparation of polydopamine (PDA) hollow capsules by templating silica particles which were subsequently removed by a PDA mediated water dissolution process without using any harsh chemical treatment. It was found that the time required for silica removal varied depending on the PDA coating and dissolution conditions. Factors that could influence the core removal process including the PDA thickness and coating temperature, silica calcination duration and the availability of water were then examined in detail. Additionally, catalase was used as a model enzyme to be encapsulated into PDA hollow capsules and its bio-functionality was found to remain active. The bioactivity test results also indicated that the as-synthesized PDA capsules possessed a porous structure, which allows the penetration of small molecules such as H2O2. This study offers a better insight into silica dissolution process that mediated by PDA and contributes to the development of an eco-friendly approach for the fabrication of hollow capsules that have promising applications in drug delivery systems.

19.
Angew Chem Int Ed Engl ; 58(13): 4227-4231, 2019 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-30773762

RESUMO

The integration of heterometallic units and nanostructures into metal-organic frameworks (MOFs) used for the oxygen evolution reaction (OER) can enhance the electrocatalytic performance and help elucidate underlying mechanisms. We have synthesized a series of stable MOFs (CTGU-10a1-d1) based on trinuclear metal carboxylate clusters and a hexadentate carboxylate ligand with a (6,6)-connected nia net. We also present a strategy to synthesize hierarchical bimetallic MOF nanostructures (CTGU-10a2-d2). Among these, CTGU-10c2 is the best material for the OER, with an overpotential of 240 mV at a current density of 10 mA cm-2 and a Tafel slope of 58 mV dec-1 . This is superior to RuO2 and confirms CTGU-10c2 as one of the few known high-performing pure-phase MOF-OER electrocatalysts. Notably, bimetallic CTGU-10b2 and c2 show an improved OER activity over monometallic CTGU-10a2 and d2. Both DFT and experiments show that the remarkable OER performance of CTGU-10c2 is due to the presence of unsaturated metal sites, a hierarchical nanobelt architecture, and the Ni-Co coupling effect.

20.
Materials (Basel) ; 12(3)2019 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-30709007

RESUMO

BaTiO3/polymer/Al (BPA) composite films for energy storage were fabricated by way of a roll coating and thermal curing process. The coating slurry consisted of silicon-containing heat-resistant resin (CYN-01) and BaTiO3 particles with various particle sizes obtained from commercial BaTiO3 powders processed at different durations of wet sand grinding in the presence of silane coupling agent (KH550), which not only improves the dielectric performance of the BPA films but also facilitates its production in a large scale. The major influence factors, such as the ratio between BaTiO3 and resin and the size of BaTiO3 particles, were investigated and their related mechanisms were discussed. The results show that modifying BaTiO3 particles (D90 = 0.83 µm) with the silane coupling agent of KH550 enhances the dielectric properties of the BPA films. The typical BPA films obtained exhibit a high dielectric constant of 32, a high break strength of 20.8 V/µm and a low dielectric loss of 0.014. The present work provides a simple and convenient way to prepare high-quality ceramic/polymer composite films for energy-storage application in a large scale.

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