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1.
ChemSusChem ; 13(7): 1900-1905, 2020 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-31944610

RESUMO

Enzyme catalysts always show an excellent catalytic selectivity, which is important in biochemistry, especially in catalytic synthesis and biopharming. This selectivity is achieved by combining the binding effect induced by the electrostatic effect of the enzyme to attract a specific substrate and then the prearrangement of the substrates inside the enzyme pocket. Herein, we report a proof-of-concept application of an interfacial electrostatic field induced by constructing Schottky heterojunctions to mimic the electrostatic catalysis of an enzyme. In combination with the 3 D structure, a transition metal/carbon dyad was designed by nanoconfinement methods to promote the differential binding effect and the space-induced organization of the reaction intermediate (vanillyl alcohol) to develop a new one-step hydrogenolysis of vanillin for the production of 2-methoxy-4-methylphenol with a remarkably high selectivity (>99 %).

2.
Nat Commun ; 10(1): 4380, 2019 09 26.
Artigo em Inglês | MEDLINE | ID: mdl-31558716

RESUMO

Production of ammonia is currently realized by the Haber-Bosch process, while electrochemical N2 fixation under ambient conditions is recognized as a promising green substitution in the near future. A lack of efficient electrocatalysts remains the primary hurdle for the initiation of potential electrocatalytic synthesis of ammonia. For cheaper metals, such as copper, limited progress has been made to date. In this work, we boost the N2 reduction reaction catalytic activity of Cu nanoparticles, which originally exhibited negligible N2 reduction reaction activity, via a local electron depletion effect. The electron-deficient Cu nanoparticles are brought in a Schottky rectifying contact with a polyimide support which retards the hydrogen evolution reaction process in basic electrolytes and facilitates the electrochemical N2 reduction reaction process under ambient aqueous conditions. This strategy of inducing electron deficiency provides new insight into the rational design of inexpensive N2 reduction reaction catalysts with high selectivity and activity.

3.
ACS Appl Mater Interfaces ; 11(38): 34922-34929, 2019 Sep 25.
Artigo em Inglês | MEDLINE | ID: mdl-31476855

RESUMO

Self-supported aerogel composed of carbon nitride nanolayers can act as a bifunctional photocatalyst and show enhanced photoreduction and photooxidation performance due to the large surface areas and nitrogen vacancies. The carbon nitride aerogel can catalyze hydrogen evolution at a rate of nearly 4.2 mmol h-1 g-1 and oxidize benzyl alcohols with a high conversion efficiency and selectivity under milder conditions. Note that the activity of carbon nitride aerogel for photochemical alcohol oxidation shows outstanding performance compared with carbon nitride based photocatalysts. Both density functional theory and experimental results demonstrate that the introduction of nitrogen vacancies within the carbon nitride aerogel contributes to the formation of a crooked structure and enhanced adsorption of oxygen compared with a bulk sample.

4.
Chem Commun (Camb) ; 55(27): 3971-3974, 2019 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-30874700

RESUMO

We described an effective way to generate a Co3O4 mesocrystal array with well-developed porosity, simply by uniting a coupled interface with hydrazine treatment. Due to the fast electron transfer and sufficient active sites, the Ti mesh-supported Co3O4 nanoneedles electrode could provide a current density of 49.9 mA cm-2 at 570 mV OER overpotential and has exceptionally high stability.

5.
J Am Chem Soc ; 141(1): 38-41, 2019 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-30525578

RESUMO

Highly efficient fixation of CO2 for the synthesis of useful organic carbonates has drawn much attention. The design of sustainable Lewis acid-base pairs, which has mainly relied on expensive organic ligands, is the key challenge in the activation of the substrate and CO2 molecule. Here, we report the application of Mott-Schottky type nanohybrids composed of electron-deficient Cu and electron-rich N-doped carbon for CO2 fixation. A ligand-free and additive-free method was used to boost the basicity of the carbon supports and the acidity of Cu by increasing the Schottky barrier at their boundary, mimicking the beneficial function of organic ligands acting as the Lewis acid and base in metal-organic frameworks (MOFs) or polymers and simultaneously avoiding the possible deactivation associated with the necessary stability of a heterogeneous catalyst. The optimal Cu/NC-0.5 catalyst exhibited a remarkably high turnover frequency (TOF) value of 615 h-1 at 80 °C, which is 10 times higher than that of the state-of-the-art metal-based heterogeneous catalysts in the literature.

6.
Angew Chem Int Ed Engl ; 57(46): 15194-15198, 2018 Nov 12.
Artigo em Inglês | MEDLINE | ID: mdl-30251296

RESUMO

As a new type of heterogeneous catalyst with "homogeneous-like" activity, single-site transition-metal materials are usually treated as integrated but separate active centers. A novel grouping effect is reported for single Ni-N4 sites in nitrogen-doped carbon (Ni/NC), where an effective ligand-stabilized polycondensation method endows Ni/NC nanocatalysts with a high content of single-site Ni up to 9.5 wt %. The enhanced electron density at each single Ni-N4 site promotes a highly efficient hydrogen transfer, which is exemplified by the coupling of benzyl alcohol and aniline into N-benzylaniline with a turnover frequency (TOF) value of 7.0 molN-benzylaniline molmetal -1 h-1 ; this TOF outpaces that of reported stable non-noble-metal-based catalysts by a factor of 2.

7.
Angew Chem Int Ed Engl ; 57(38): 12563-12566, 2018 Sep 17.
Artigo em Inglês | MEDLINE | ID: mdl-30070752

RESUMO

The exploitation of metal-free organic polymers as electrodes for water splitting reactions is limited by their presumably low activity and poor stability, especially for the oxygen evolution reaction (OER) under more critical conditions. Now, the thickness of a cheap and robust polymer, poly(p-phenylene pyromellitimide) (PPPI) was rationally engineered by an in situ polymerization method to make the metal-free polymer available for the first time as flexible, tailorable, efficient, and ultra-stable electrodes for water oxidation over a wide pH range. The PPPI electrode with an optimized thickness of about 200 nm provided a current density of 32.8 mA cm-2 at an overpotential of 510 mV in 0.1 mol L-1 KOH, which is even higher than that (31.5 mA cm-2 ) of commercial IrO2 OER catalyst. The PPPI electrodes are scalable and stable, maintaining 92 % of its activity after a 48-h chronoamperometric stability test.

8.
ChemSusChem ; 11(14): 2306-2309, 2018 Jul 20.
Artigo em Inglês | MEDLINE | ID: mdl-29851293

RESUMO

Electrochemical gas evolution and activation reactions are complicated processes, involving not only active electrocatalysts but also the interaction among solid electrodes, electrolyte, and gas-phase products and reactants. In this study, multiphase interfaces of superadsorbing graphene-based electrodes were controlled without changing the active centers to significantly facilitate mass diffusion kinetics for superior performance. The achieved in-depth understanding of how to regulate the interfacial properties to promote the electrochemical performance could provide valuable clues for electrode manufacture and for the design of more active electrocatalysts.

9.
Biochimie ; 148: 46-54, 2018 May.
Artigo em Inglês | MEDLINE | ID: mdl-29501482

RESUMO

A novel extracellular laccase was purified from fermentation broth of the white rot fungus Trametes sp. F1635 by a three-step protocol including two consecutive ion-exchange chromatography steps on DEAE-Sepharose and SP-Sepharose, and a final gel-filtration on Superdex 75. The purified laccase (TsL) was a monomeric protein with the molecular mass of 64.8 kDa. It demonstrated high oxidation activity of 4.00 × 104 U/mg towards ABTS. Its N-terminal amino acid sequence was AIGPVADLTIINNAV which was unique and sharing high similarity of other fungal laccases. TsL was a yellow laccase based on absorption spectrum analysis. It demonstrated an acidic pH optimum of 2.6 and temperature optimum of 50 °C towards ABTS. The Km and Vmax values towards ABTS were estimated to 18.58 µM and 1.35 µmol/min, respectively. TsL manifested effective decolorization activity towards eriochrome black T (EBT), remazol brilliant blue R (RBBR), malachite green (MG), and eriochrome black T (EBT) (over 60%). Violuric acid (VA) and acetosyringone (AS) were the optimal mediators for the laccase in dye decolorization. Results suggest that TsL demonstrates great potential for dye decolorization and water treatment.


Assuntos
Corantes/metabolismo , Espaço Extracelular/enzimologia , Lacase/metabolismo , Trametes/citologia , Sequência de Aminoácidos , Cor , Fermentação , Concentração de Íons de Hidrogênio , Cinética , Lacase/química , Peso Molecular , Temperatura , Trametes/enzimologia
10.
Chem Commun (Camb) ; 53(76): 10544-10547, 2017 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-28890982

RESUMO

The oxygen evolution reaction (OER) is the rate-limiting process for water splitting, and highly efficient large-area OER photoanodes have been considered as an essential part in photoelectrochemical water splitting reactors. The high hole-electron separation efficiency of photoanodes is highly required for real applications of photoanodes in sufficiently harvesting solar energy. Herein we show that the inactive g-C3N4 nanolayers can be self-assembled with BiVO4 into a highly coupled BV/CN dyad to significantly enhance the charge separation efficiency of BiVO4 photoelectrodes for the OER. The incident photon-to-current conversion efficiency (IPCE) of visible light (400 nm) provided by the scalable BV/CN-5 photoanode was estimated to be 50% at 1.23 V vs. RHE in 0.5 M Na2SO4 solution and significantly increased to 97% at a bias voltage of 1.6 V vs. RHE.

11.
ChemSusChem ; 10(14): 2875-2879, 2017 07 21.
Artigo em Inglês | MEDLINE | ID: mdl-28612461

RESUMO

Oxygen vacancies can help to capture oxygen-containing species and act as active centers for oxygen evolution reaction (OER). Unfortunately, effective methods for generating a high amount of oxygen vacancies on the surface of various nanocatalysts are rather limited. Here, we described an effective way to generate oxygen-vacancy-rich surface of transition metal oxides, exemplified with Co3 O4 , simply by constructing highly coupled interface of ultrafine Co3 O4 nanocrystals and metallic Ti. Impressively, the amounts of oxygen vacancy on the surface of Co3 O4 /Ti surpassed the reported values of the Co3 O4 modified even under highly critical conditions. The Co3 O4 /Ti electrode could provide a current density of 23 mA cm-2 at an OER overpotential of 570 mV, low Tafel slope, and excellent durability in neutral medium. Because of the formation of a large amount of oxygen vacancies as the active centers for OER on the surface, the TOF value of the Co3 O4 @Ti electrode was optimized to be 3238 h-1 at an OER overpotential of 570 mV, which is 380 times that of the state-of-the-art non-noble nanocatalysts in the literature.


Assuntos
Cobalto/química , Nanopartículas/química , Nanotecnologia , Óxidos/química , Oxigênio/química , Titânio/química , Água/química , Animais , Eletroquímica , Eletrodos , Engenharia , Oxirredução
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