scholarly journals WS2 moiré superlattices derived from mechanical flexibility for hydrogen evolution reaction

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Lingbin Xie ◽  
Longlu Wang ◽  
Weiwei Zhao ◽  
Shujuan Liu ◽  
Wei Huang ◽  
...  
Keyword(s):  
Active Sites ◽  
Hydrogen Adsorption ◽  
Theoretical Calculations ◽  
Catalytic Performance ◽  
Emergent Properties ◽  
Mechanical Instability ◽  
Synthetic Strategy ◽  
Exciting Opportunity ◽  
Catalytic Hydrogen ◽  
One Step

AbstractThe discovery of moiré superlattices (MSLs) opened an era in the research of ‘twistronics’. Engineering MSLs and realizing unique emergent properties are key challenges. Herein, we demonstrate an effective synthetic strategy to fabricate MSLs based on mechanical flexibility of WS2 nanobelts by a facile one-step hydrothermal method. Unlike previous MSLs typically created through stacking monolayers together with complicated method, WS2 MSLs reported here could be obtained directly during synthesis of nanobelts driven by the mechanical instability. Emergent properties are found including superior conductivity, special superaerophobicity and superhydrophilicity, and strongly enhanced electro-catalytic activity when we apply ‘twistronics’ to the field of catalytic hydrogen production. Theoretical calculations show that such excellent catalytic performance could be attributed to a closer to thermoneutral hydrogen adsorption free energy value of twisted bilayers active sites. Our findings provide an exciting opportunity to design advanced WS2 catalysts through moiré superlattice engineering based on mechanical flexibility.

scholarly journals Platinum–copper single atom alloy catalysts with high performance towards glycerol hydrogenolysis

2019 ◽  
Vol 10 (1) ◽  
Author(s):  
Xi Zhang ◽  
Guoqing Cui ◽  
Haisong Feng ◽  
Lifang Chen ◽  
Hui Wang ◽  
...  
Keyword(s):  
Active Sites ◽  
High Performance ◽  
Reaction Pathway ◽  
Theoretical Calculations ◽  
Experimental Studies ◽  
Value Added ◽  
Catalytic Performance ◽  
Single Atom ◽  
Glycerol Hydrogenolysis ◽  
Single Atom Alloy

AbstractSelective hydrogenolysis of biomass-derived glycerol to propanediol is an important reaction to produce high value-added chemicals but remains a big challenge. Herein we report a PtCu single atom alloy (SAA) catalyst with single Pt atom dispersed on Cu nanoclusters, which exhibits dramatically boosted catalytic performance (yield: 98.8%) towards glycerol hydrogenolysis to 1,2-propanediol. Remarkably, the turnover frequency reaches up to 2.6 × 103 molglycerol·molPtCu–SAA−1·h−1, which is to our knowledge the largest value among reported heterogeneous metal catalysts. Both in situ experimental studies and theoretical calculations verify interface sites of PtCu–SAA serve as intrinsic active sites, in which the single Pt atom facilitates the breakage of central C–H bond whilst the terminal C–O bond undergoes dissociation adsorption on adjacent Cu atom. This interfacial synergistic catalysis based on PtCu–SAA changes the reaction pathway with a decreased activation energy, which can be extended to other noble metal alloy systems.

scholarly journals Liquid-phase Exfoliated Two-dimensional Bi Nanosheet as a Durable Electrocatalyst for Hydrogen Evolution Reaction

2021 ◽  
Author(s):  
Chenguang Duan ◽  
Huating Liu ◽  
Zongyu Huang ◽  
Hui Qiao ◽  
Yang Zhou ◽  
...  
Keyword(s):  
Liquid Phase ◽  
Hydrogen Evolution ◽  
Hydrogen Evolution Reaction ◽  
Large Scale ◽  
Hydrogen Adsorption ◽  
Theoretical Calculations ◽  
Cost Effective ◽  
Catalytic Performance ◽  
Hydrogen Energy ◽  
Two Dimensional

Abstract Electrocatalytic hydrogen evolution is an exercisable way to achieve large-scale application of hydrogen energy. It is of great significance to develop an effect, stable and cost-effective electrocatalyst. Here, we applied the two-dimensional (2D) bismuth (Bi) to the electrocatalytic hydrogen evolution, and proposed the strategies to enhance the catalytic performance of the catalyst. The exfoliated Bi nanosheets via sonication assisted liquid-phase exfoliation display higher electrocatalytic activity (overpotential of -958 mV vs RHE at 10 mA cm− 2) compared to the bulk counterpart. Theoretical calculations about Gibbs free energy from the hydrogen adsorption for 1 layer, 2 layers and 5 layers Bi also manifest the decrease of thickness is favorable for hydrogen evolution reaction (HER). To further evaluate the electrocatalytic performance of Bi nanosheets, the typical parameters measured in different H+ concentration (C[H+]) are carried out. The improved catalytic activity obtained in 0.5 M H2SO4 is attributed to enhancing the hydrogen adsorption and accelerating the charge transport on the surface of catalyst. Moreover, the durability of Bi nanosheets electrode has been texted, where the current is not evident fluctuation during the 40000 s electrolysis measurement indicating its excellent stability. The present work expands the application of Bi in the catalysis and provides the simple strategies to improve its hydrogen evolution performance.

scholarly journals Single-atom nanozymes

2019 ◽  
Vol 5 (5) ◽  
pp. eaav5490 ◽  
Author(s):  
Liang Huang ◽  
Jinxing Chen ◽  
Linfeng Gan ◽  
Jin Wang ◽  
Shaojun Dong
Keyword(s):  
Active Sites ◽  
Synergistic Effects ◽  
Theoretical Calculations ◽  
Experimental Studies ◽  
Size Composition ◽  
Underlying Mechanism ◽  
Catalytic Performance ◽  
Axial Ligand ◽  
Single Atom ◽  
Active Centers

Conventional nanozyme technologies face formidable challenges of intricate size-, composition-, and facet-dependent catalysis and inherently low active site density. We discovered a new class of single-atom nanozymes with atomically dispersed enzyme-like active sites in nanomaterials, which significantly enhanced catalytic performance, and uncovered the underlying mechanism. With oxidase catalysis as a model reaction, experimental studies and theoretical calculations revealed that single-atom nanozymes with carbon nanoframe–confined FeN5 active centers (FeN5 SA/CNF) catalytically behaved like the axial ligand–coordinated heme of cytochrome P450. The definite active moieties and crucial synergistic effects endow FeN5 SA/CNF with a clear electron push-effect mechanism, as well as the highest oxidase-like activity among other nanozymes (the rate constant is 70 times higher than that of commercial Pt/C) and versatile antibacterial applications. These suggest that the single-atom nanozymes have great potential to become the next-generation nanozymes.

One-step synthesis of cobalt-doped MoS2 nanosheets as bifunctional electrocatalysts for overall water splitting under both acidic and alkaline conditions

2018 ◽  
Vol 54 (31) ◽  
pp. 3859-3862 ◽  
Author(s):  
Qizhong Xiong ◽  
Xian Zhang ◽  
Haojie Wang ◽  
Guoqiang Liu ◽  
Guozhong Wang ◽  
...  
Keyword(s):  
Free Energy ◽  
Electronic Structure ◽  
Water Splitting ◽  
Active Sites ◽  
Hydrogen Adsorption ◽  
Mos2 Nanosheets ◽  
Adsorption Free Energy ◽  
Alkaline Conditions ◽  
One Step ◽  
Catalytic Active Sites

Cobalt covalent doping in MoS2 effectively regulates its electronic structure to decrease the hydrogen adsorption free energy for high HER and simultaneously contributes additional catalytic active sites for the OER.

The design and catalytic performance of molybdenum active sites on an MCM-41 framework for the aerobic oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran

2019 ◽  
Vol 9 (3) ◽  
pp. 811-821 ◽  
Author(s):  
Zhao-Meng Wang ◽  
Li-Juan Liu ◽  
Bo Xiang ◽  
Yue Wang ◽  
Ya-Jing Lyu ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Active Sites ◽  
Aerobic Oxidation ◽  
Catalytic Performance ◽  
Mcm 41

The catalytic activity decreases as –(SiO)3Mo(OH)(O) > –(SiO)2Mo(O)2 > –(O)4–MoO.

Catalytic Resonance Theory: Parallel Reaction Pathway Control

2019 ◽  
Author(s):  
M. Alexander Ardagh ◽  
Manish Shetty ◽  
Anatoliy Kuznetsov ◽  
Qi Zhang ◽  
Phillip Christopher ◽  
...  
Keyword(s):  
Chemical Reactions ◽  
Active Site ◽  
Active Sites ◽  
Reaction Pathway ◽  
Control Strategies ◽  
Oscillation Amplitude ◽  
Catalytic Performance ◽  
Parallel Reaction ◽  
Resonance Theory ◽  
Static Conditions

Catalytic enhancement of chemical reactions via heterogeneous materials occurs through stabilization of transition states at designed active sites, but dramatically greater rate acceleration on that same active site is achieved when the surface intermediates oscillate in binding energy. The applied oscillation amplitude and frequency can accelerate reactions orders of magnitude above the catalytic rates of static systems, provided the active site dynamics are tuned to the natural frequencies of the surface chemistry. In this work, differences in the characteristics of parallel reactions are exploited via selective application of active site dynamics (0 < ΔU < 1.0 eV amplitude, 10<sup>-6</sup> < f < 10<sup>4</sup> Hz frequency) to control the extent of competing reactions occurring on the shared catalytic surface. Simulation of multiple parallel reaction systems with broad range of variation in chemical parameters revealed that parallel chemistries are highly tunable in selectivity between either pure product, even when specific products are not selectively produced under static conditions. Two mechanisms leading to dynamic selectivity control were identified: (i) surface thermodynamic control of one product species under strong binding conditions, or (ii) catalytic resonance of the kinetics of one reaction over the other. These dynamic parallel pathway control strategies applied to a host of chemical conditions indicate significant potential for improving the catalytic performance of many important industrial chemical reactions beyond their existing static performance.

Structural/Texture Evolution During Facile Substitution of Ni into ZSM-5 Nanostructure vs. its Impregnation Dispersion Used in Selective Transformation of Methanol to Ethylene and Propylene

2020 ◽  
Vol 23 ◽  
Author(s):  
Parisa Sadeghpour ◽  
Mohammad Haghighi ◽  
Mehrdad Esmaeili
Keyword(s):  
High Temperature ◽  
Physicochemical Properties ◽  
Active Sites ◽  
Catalytic Performance ◽  
Fixed Bed Reactor ◽  
Light Olefins ◽  
Isomorphous Substitution ◽  
Impregnation Method ◽  
Hydrothermal Temperature ◽  
X Ray

Aim and Objective: Effect of two different modification methods for introducing Ni into ZSM-5 framework was investigated under high temperature synthesis conditions. The nickel successfully introduced into the MFI structures at different crystallization conditions to enhance the physicochemical properties and catalytic performance. Materials and Methods: A series of impregnated Ni/ZSM-5 and isomorphous substituted NiZSM-5 nanostructure catalysts were prepared hydrothermally at different high temperatures and within short times. X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), Energy dispersive X-ray (EDX), Brunner, Emmett and Teller-Barrett, Joyner and Halenda (BET-BJH), Fourier transform infrared (FTIR) and Temperature-programmed desorption of ammonia (TPDNH3) were applied to investigate the physicochemical properties. Results: Although all the catalysts showed pure silica MFI–type nanosheets and coffin-like morphology, using the isomorphous substitution for Ni incorporation into the ZSM-5 framework led to the formation of materials with lower crystallinity, higher pore volume and stronger acidity compared to using impregnation method. Moreover, it was found that raising the hydrothermal temperature increased the crystallinity and enhanced more uniform incorporation of Ni atoms in the crystalline structure of catalysts. TPD-NH3 analysis demonstrated that high crystallization temperature and short crystallization time of NiZSM-5(350-0.5) resulted in fewer weak acid sites and medium acid strength. The MTO catalytic performance was tested in a fixed bed reactor at 460ºC and GHSV=10500 cm3 /gcat.h. A slightly different reaction pathway was proposed for the production of light olefins over impregnated Ni/ZSM-5 catalysts based on the role of NiO species. The enhanced methanol conversion for isomorphous substituted NiZSM-5 catalysts could be related to the most accessible active sites located inside the pores. Conclusion: The impregnated Ni/ZSM-5 catalyst prepared at low hydrothermal temperature showed the best catalytic performance, while the isomorphous substituted NiZSM-5 prepared at high temperature was found to be the active molecular sieve regarding the stability performance.

Efficient Production of Biodiesel Catalyzed by Acidic Nanoporous Carbon Materials：A Review

2020 ◽  
Vol 16 ◽  
Author(s):  
Anping Wang ◽  
Heng Zhang ◽  
Hu Li ◽  
Song Yang
Keyword(s):  
Pore Structure ◽  
Active Sites ◽  
Catalytic Performance ◽  
Nanoporous Carbon ◽  
Biodiesel Production ◽  
Efficient Production ◽  
Fossil Energy ◽  
Catalytic Materials ◽  
High Acid ◽  
Carbon Based

Background: With the gradual decrease of fossil energy, the development of alternatives to fossil energy has attracted more and more attention. Biodiesel is considered to be the most potent alternative to fossil energy, mainly due to its green, renewable and biodegradable advantages. The stable, efficient and reusable catalysts are undoubtedly the most critical in the preparation of biodiesel. Among them, nanoporous carbon-based acidic materials are very important biodiesel catalysts. Objective: The latest advances of acidic nanoporous carbon catalysts in biodiesel production was reviewed. Methods: Biodiesel is mainly synthesized by esterification and transesterification. Due to the important role of nanoporous carbon-based acidic materials in the catalytic preparation of biodiesel, we focused on the synthesis, physical and chemical properties, catalytic performance and reusability. Results: Acidic catalytic materials have a good catalytic performance for high acid value feedstocks. However, the preparation of biodiesel with acid catalyst requires relatively strict reaction conditions. The application of nanoporous acidic carbon-based materials, due to the support of carbon-based framework, makes the catalyst have good stability and unique pore structure, accelerates the reaction mass transfer speed and accelerates the reaction. Conclusion: Nanoporous carbon-based acidic catalysts have the advantages of suitable pore structure, high active sites, and high stability. In order to make these catalytic processes more efficient, environmentally friendly and low cost, it is an important research direction for the future biodiesel catalysts to develop new catalytic materials with high specific surface area, suitable pore size, high acid density, and excellent performance.

scholarly journals Insights on forming N,O-coordinated Cu single-atom catalysts for electrochemical reduction CO2 to methane

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Yanming Cai ◽  
Jiaju Fu ◽  
Yang Zhou ◽  
Yu-Chung Chang ◽  
Qianhao Min ◽  
...  
Keyword(s):  
Energy Barrier ◽  
Active Sites ◽  
Theoretical Calculations ◽  
High Energy ◽  
Single Atom ◽  
Faradaic Efficiency ◽  
High Energy Barrier ◽  
Catalytic Sites ◽  
Electron Reduction ◽  
First Time

AbstractSingle-atom catalysts (SACs) are promising candidates to catalyze electrochemical CO2 reduction (ECR) due to maximized atomic utilization. However, products are usually limited to CO instead of hydrocarbons or oxygenates due to unfavorable high energy barrier for further electron transfer on synthesized single atom catalytic sites. Here we report a novel partial-carbonization strategy to modify the electronic structures of center atoms on SACs for lowering the overall endothermic energy of key intermediates. A carbon-dots-based SAC margined with unique CuN2O2 sites was synthesized for the first time. The introduction of oxygen ligands brings remarkably high Faradaic efficiency (78%) and selectivity (99% of ECR products) for electrochemical converting CO2 to CH4 with current density of 40 mA·cm-2 in aqueous electrolytes, surpassing most reported SACs which stop at two-electron reduction. Theoretical calculations further revealed that the high selectivity and activity on CuN2O2 active sites are due to the proper elevated CH4 and H2 energy barrier and fine-tuned electronic structure of Cu active sites.

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