Rational design of ornithine decarboxylase with high catalytic activity for the production of putrescine

The synthesis of support materials with suitable coordination sites and confined structures for the controlled growth of ultrasmall metal nanoparticles is of great importance in heterogeneous catalysis. Here, by rational design of a cross-linked β-cyclodextrin polymer network (CPN), various metal nanoparticles (palladium, silver, platinum, gold, and rhodium) of subnanometer size (<1 nm) and narrow size distribution are formed via a mild and facile procedure. The presence of the metal coordination sites and the network structure are key to the successful synthesis and stabilization of the ultrasmall metal nanoparticles. The as-prepared CPN, loaded with palladium nanoparticles, is used as a heterogeneous catalyst and shows outstanding catalytic performance in the hydrogenation of nitro compounds and Suzuki-Miyaura coupling reaction under mild conditions. The CPN support works synergistically with the metal nanoparticles, achieving high catalytic activity and selectivity. In addition, the catalytic activity of the formed catalyst is controllable.

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Rational design of metal/N-doped carbon nanocatalysts via sol-gel method for obtaining high catalytic activity toward reduction reactions of 4-nitrophenol and Rhodamine B

Applied Catalysis A General ◽

10.1016/j.apcata.2022.118479 ◽

2022 ◽

pp. 118479

Author(s):

Pingyun Li ◽

Han Wang ◽

Shengxiang Jiang ◽

Jinling Wang ◽

Zhenhua Cao ◽

...

Keyword(s):

Catalytic Activity ◽

Rhodamine B ◽

Rational Design ◽

Sol Gel ◽

High Catalytic Activity ◽

Reduction Reactions ◽

Gel Method ◽

Sol Gel Method

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Computationally Generated Maps of Surface Structures and Catalytic Activities for Alloy Phase Diagrams

10.26434/chemrxiv.8311865.v1 ◽

2019 ◽

Author(s):

Liang Cao ◽

Le, Niu ◽

Tim Mueller

Keyword(s):

Phase Diagram ◽

Catalytic Activity ◽

Oxygen Reduction Reaction ◽

Oxygen Reduction ◽

Rational Design ◽

Intermetallic Phase ◽

Reduction Reaction ◽

Alloy Surface ◽

High Catalytic Activity ◽

Highly Active

To facilitate the rational design of alloy catalysts, we introduce a method for rapidly calculating the structure and catalytic properties of a substitutional alloy surface that is in equilibrium with the underlying bulk phase. We implement our method by developing a way to generate surface cluster expansions that explicitly account for the lattice parameter of the bulk structure. This approach makes it possible to computationally map the structure and catalytic activity of an alloy surface at every point in the alloy phase diagram, enabling the identification of synthesis conditions likely to result in highly active catalysts. We demonstrate our approach by analyzing Pt-rich Pt–Ni catalysts for the oxygen reduction reaction, finding two regions in the phase diagram that are predicted to result in highly active catalysts. Our analysis indicates that the Pt3Ni(111) surface, which has the highest known specific activity for the oxygen reduction reaction, is likely able to achieve its high activity through the formation of an intermetallic phase with L12 order. We use the generated surface structure and catalytic activity maps to demonstrate how the intermetallic nature of this phase leads to high catalytic activity and discuss how the underlying principles can be used in catalysis design. We further discuss the importance of surface phases and demonstrate how they can dramatically affect catalytic activity.

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Improved methanol tolerance of Rhizomucor miehei lipase based on N‑glycosylation within the α-helix region and its application in biodiesel production

Biotechnology for Biofuels ◽

10.1186/s13068-021-02087-6 ◽

2021 ◽

Vol 14 (1) ◽

Author(s):

Miao Tian ◽

Lingmei Yang ◽

Zhiyuan Wang ◽

Pengmei Lv ◽

Junying Fu ◽

...

Keyword(s):

Catalytic Activity ◽

Rational Design ◽

Rhizomucor Miehei ◽

Raw Material ◽

Biodiesel Production ◽

High Catalytic Activity ◽

Single Chain ◽

Methanol Tolerance ◽

First Choice ◽

Α Helix

Abstract Background Liquid lipases are widely used to convert oil into biodiesel. Methanol-resistant lipases with high catalytic activity are the first choice for practical production. Rhizomucor miehei lipase (RML) is a single-chain α/β-type protein that is widely used in biodiesel preparation. Improving the catalytic activity and methanol tolerance of RML is necessary to realise the industrial production of biodiesel. Results In this study, a semi-rational design method was used to optimise the catalytic activity and methanol tolerance of ProRML. After N-glycosylation modification of the α-helix of the mature peptide in ProRML, the resulting mutants N218, N93, N115, N260, and N183 increased enzyme activity by 66.81, 13.54, 10.33, 3.69, and 2.39 times than that of WT, respectively. The residual activities of N218 and N260 were 88.78% and 86.08% after incubation in 50% methanol for 2.5 h, respectively. In addition, the biodiesel yield of all mutants was improved when methanol was added once and reacted for 24 h with colza oil as the raw material. N260 and N218 increased the biodiesel yield from 9.49% to 88.75% and 90.46%, respectively. Conclusions These results indicate that optimising N-glycosylation modification in the α-helix structure is an effective strategy for improving the performance of ProRML. This study provides an effective approach to improve the design of the enzyme and the properties of lipase mutants, thereby rendering them suitable for industrial biomass conversion.

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Computationally Generated Maps of Surface Structures and Catalytic Activities for Alloy Phase Diagrams

10.26434/chemrxiv.8311865.v2 ◽

2019 ◽

Author(s):

Liang Cao ◽

Le, Niu ◽

Tim Mueller

Keyword(s):

Phase Diagram ◽

Catalytic Activity ◽

Oxygen Reduction Reaction ◽

Oxygen Reduction ◽

Rational Design ◽

Intermetallic Phase ◽

Reduction Reaction ◽

Alloy Surface ◽

High Catalytic Activity ◽

Highly Active

To facilitate the rational design of alloy catalysts, we introduce a method for rapidly calculating the structure and catalytic properties of a substitutional alloy surface that is in equilibrium with the underlying bulk phase. We implement our method by developing a way to generate surface cluster expansions that explicitly account for the lattice parameter of the bulk structure. This approach makes it possible to computationally map the structure and catalytic activity of an alloy surface at every point in the alloy phase diagram, enabling the identification of synthesis conditions likely to result in highly active catalysts. We demonstrate our approach by analyzing Pt-rich Pt–Ni catalysts for the oxygen reduction reaction, finding two regions in the phase diagram that are predicted to result in highly active catalysts. Our analysis indicates that the Pt3Ni(111) surface, which has the highest known specific activity for the oxygen reduction reaction, is likely able to achieve its high activity through the formation of an intermetallic phase with L12 order. We use the generated surface structure and catalytic activity maps to demonstrate how the intermetallic nature of this phase leads to high catalytic activity and discuss how the underlying principles can be used in catalysis design. We further discuss the importance of surface phases and demonstrate how they can dramatically affect catalytic activity.

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Enhanced catalytic activity of low-Pt content nanocatalysts supported on hollow carbon spheres for the ORR in alkaline media

MRS Advances ◽

10.1557/adv.2020.370 ◽

2020 ◽

Vol 5 (57-58) ◽

pp. 2961-2972

Author(s):

P.C. Meléndez-González ◽

E. Garza-Duran ◽

J.C. Martínez-Loyola ◽

P. Quintana-Owen ◽

I.L. Alonso-Lemus ◽

...

Keyword(s):

Catalytic Activity ◽

Anion Exchange ◽

Average Particle Size ◽

Synthesis Method ◽

Alkaline Media ◽

High Catalytic Activity ◽

Average Particle ◽

Carbon Spheres ◽

Hollow Carbon ◽

Hollow Carbon Spheres

In this work, low-Pt content nanocatalysts (≈ 5 wt. %) supported on Hollow Carbon Spheres (HCS) were synthesized by two routes: i) colloidal conventional polyol, and ii) surfactant-free Bromide Anion Exchange (BAE). The nanocatalysts were labelled as Pt/HCS-P and Pt/HCS-B for polyol and BAE, respectively. The physicochemical characterization of the nanocatalysts showed that by following both methods, a good control of chemical composition was achieved, obtaining in addition well dispersed nanoparticles of less than 3 nm TEM average particle size (d) on the HCS. Pt/HCS-B contained more Pt0 species than Pt/HCS-P, an effect of the synthesis method. In addition, the structure of the HCS remains more ordered after BAE synthesis, compared to polyol. Regarding the catalytic activity for the Oxygen Reduction Reaction (ORR) in 0.5 M KOH, Pt/HCS-P and Pt/HCS-B showed a similar performance in terms of current density (j) at 0.9 V vs. RHE than the benchmark commercial 20 wt. % Pt/C. However, Pt/HCS-P and Pt/HCS-B demonstrated a 6 and 5-fold increase in mass catalytic activity compared to Pt/C, respectively. A positive effect of the high specific surface area of the HCS and its interactions with metal nanoparticles and electrolyte, which promoted the mass transfer, increased the performance of Pt/HCS-P and Pt/HCS-B. The high catalytic activity showed by Pt/HCS-B and Pt/HCS-P for the ORR, even with a low-Pt content, make them promising cathode nanocatalysts for Anion Exchange Membrane Fuel Cells (AEMFC).

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Ordered Intermetallic Nanoparticles with High Catalytic Activity Prepared by an Electrochemically Induced Phase Transformation

10.26434/chemrxiv.8289812 ◽

2019 ◽

Author(s):

Du Sun ◽

yunfei wang ◽

Kenneth Livi ◽

chuhong wang ◽

ruichun luo ◽

...

Keyword(s):

Catalytic Activity ◽

Diffusion Mechanism ◽

Reduction Reaction ◽

Atomic Scale ◽

High Catalytic Activity ◽

Ambient Conditions ◽

Magnetic Devices ◽

Disordered Alloys ◽

Ordered Intermetallic ◽

Intermetallic Nanoparticles

<div> The synthesis of alloys with long range atomic scale ordering (ordered intermetallics) is an emerging field of nanochemistry. Ordered intermetallic nanoparticles are useful for a wide variety of applications such as catalysis, superconductors, and magnetic devices. However, the preparation of nanostructured ordered intermetallics is challenging in comparison to disordered alloys, hindering progress in materials development. We report a process for converting colloidally synthesized ordered intermetallic PdBi2 to ordered intermetallic Pd3Bi nanoparticles under ambient conditions by an electrochemically induced phase transition. The low melting point of PdBi2 corresponds to low vacancy formation energies which enables the facile removal of the Bi from the surface, while simultaneously enabling interdiffusion of the constituent atoms via a vacancy diffusion mechanism under ambient conditions. The resulting phase-converted ordered intermetallic Pd3Bi exhibits 11x and 3.5x higher mass activty and high methanol tolerance for the oxygen reduction reaction compared to Pt/C and Pd/C, respectively,which is the highest reported for a Pd-based catalyst, to the best of our knowledge. These results establish a key development in the synthesis of noble metal rich ordered intermetallic phases with high catalytic activity, and sets forth guidelines for the design of ordered intermetallic compounds under ambient conditions. </div>

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Nickel (II) and oxovanadium (IV) complexes supported on MCM-41 mesoporous and their application in catalytic selective sulfide and thiol oxidation

Combinatorial Chemistry & High Throughput Screening ◽

10.2174/1386207323999201111192649 ◽

2020 ◽

Vol 23 ◽

Author(s):

Mohsen Nikoorazm ◽

Maryam Khanmoradi ◽

Masoumeh Sayadian

Keyword(s):

Catalytic Activity ◽

Room Temperature ◽

Sol Gel ◽

Reaction Times ◽

Significant Loss ◽

Spectral Studies ◽

High Catalytic Activity ◽

Catalytic Systems ◽

Solvent Free Conditions ◽

Mcm 41

Introduction:: MCM-41 was synthesized using the sol-gel method. Then two new transition metal complexes of Nickel (II) and Vanadium (IV), were synthesized by immobilization of adenine (6-aminopurine) into MCM-41 mesoporous. The compounds have been characterized by XRD, TGA, SEM, AAS and FT-IR spectral studies. Using these catalysts provided an efficient and enantioselective procedure for oxidation of sulfides to sulfoxides and oxidative coupling of thiols to their corresponding disulfides using hydrogen peroxide at room temperature. Materials and Methods:: To a solution of sulfide or thiol (1 mmol) and H2O2 (5 mmol), a determined amount of the catalyst was added. The reaction mixture was stirred at room temperature for the specific time under solvent free conditions. The progress of the reaction was monitored by TLC using n-hexane: acetone (8:2). Afterwards, the catalyst was removed from the reaction mixture by centrifugation and, then, washed with dichloromethane in order to give the pure products. Results:: All the products were obtained in excellent yields and short reaction times indicating the high activity of the synthesized catalysts. Besides, the catalysts can be recovered and reused for several runs without significant loss in their catalytic activity. Conclusion:: These catalytic systems furnish the products very quickly with excellent yields and VO-6AP-MCM-41 shows high catalytic activity compared to Ni-6AP-MCM-41.

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