scholarly journals Bimetallic Zr,Zr-Hydride Complexes in Zirconocene Catalyzed Alkene Dimerization

Molecules ◽  
2020 ◽  
Vol 25 (9) ◽  
pp. 2216
Author(s):  
Lyudmila V. Parfenova ◽  
Pavel V. Kovyazin ◽  
Almira Kh. Bikmeeva
Keyword(s):  
High Performance ◽  
Direct Evidence ◽  
Catalytic Performance ◽  
High Yield ◽  
Nmr Studies ◽  
Catalytic Systems ◽  
Synthetic Compounds ◽  
Precise Control ◽  
Hydride Complexes ◽  
Active Intermediates

Being valuable precursors in the production of adhesives, lubricants, and other high-performance synthetic compounds, alkene dimers and oligomers can be obtained using homogeneous zirconocene catalytic systems. Further advances in such systems require precise control of their activity and chemoselectivity, increasing both the purity and yield of the products. This relies on the process mechanism usually built around the consideration of the hydride complexes as active intermediates in the alkene di- and oligomerization; however, the majority of studies lack the direct evidence of their involvement. Parallel studies on a well-known Cp2ZrCl2-AlR3 or HAlBui2 and a novel [Cp2ZrH2]2-ClAlR2 (R = Me, Et, Bui) systems activated by methylaluminoxane (MMAO-12) have shown a deep similarity both in the catalytic performance and intermediate composition. As a result of the NMR studies, among all the intermediates considered, we proved that new Zr,Zr- hydride complexes having the type x[Cp2ZrH2∙Cp2ZrHCl∙ClAlR2]∙yMAO appear to be specifically responsible for the alkene dimerization with high yield.

scholarly journals Enhanced and stabilized hydrogen production from methanol by ultrasmall Ni nanoclusters immobilized on defect-rich h-BN nanosheets

2020 ◽  
Vol 117 (47) ◽  
pp. 29442-29452
Author(s):  
Zhuolei Zhang ◽  
Ji Su ◽  
Ana Sanz Matias ◽  
Madeleine Gordon ◽  
Yi-Sheng Liu ◽  
...  
Keyword(s):  
Transition Metal ◽  
High Performance ◽  
Density Functional ◽  
Size Control ◽  
Catalytic Performance ◽  
Catalytic Systems ◽  
High Productivity ◽  
Design And Synthesis ◽  
High Durability ◽  
Catalytically Active

Employing liquid organic hydrogen carriers (LOHCs) to transport hydrogen to where it can be utilized relies on methods of efficient chemical dehydrogenation to access this fuel. Therefore, developing effective strategies to optimize the catalytic performance of cheap transition metal-based catalysts in terms of activity and stability for dehydrogenation of LOHCs is a critical challenge. Here, we report the design and synthesis of ultrasmall nickel nanoclusters (∼1.5 nm) deposited on defect-rich boron nitride (BN) nanosheet (Ni/BN) catalysts with higher methanol dehydrogenation activity and selectivity, and greater stability than that of some other transition-metal based catalysts. The interface of the two-dimensional (2D) BN with the metal nanoparticles plays a strong role both in guiding the nucleation and growth of the catalytically active ultrasmall Ni nanoclusters, and further in stabilizing these nanoscale Ni catalysts against poisoning by interactions with the BN substrate. We provide detailed spectroscopy characterizations and density functional theory (DFT) calculations to reveal the origin of the high productivity, high selectivity, and high durability exhibited with the Ni/BN nanocatalyst and elucidate its correlation with nanocluster size and support–nanocluster interactions. This study provides insight into the role that the support material can have both regarding the size control of nanoclusters through immobilization during the nanocluster formation and also during the active catalytic process; this twofold set of insights is significant in advancing the understanding the bottom-up design of high-performance, durable catalytic systems for various catalysis needs.

scholarly journals Recent advances in the precise control of isolated single-site catalysts by chemical methods

2018 ◽  
Vol 5 (5) ◽  
pp. 673-689 ◽  
Author(s):  
Zhijun Li ◽  
Dehua Wang ◽  
Yuen Wu ◽  
Yadong Li
Keyword(s):  
High Performance ◽  
Industrial Area ◽  
High Mass ◽  
Single Atom ◽  
Catalytic Systems ◽  
Heterogenous Catalysis ◽  
Precise Control ◽  
Recent Advances ◽  
Challenges And Opportunities ◽  
Mass Activity

Abstract The search for constructing high-performance catalysts is an unfailing topic in chemical fields. Recently, we have witnessed many breakthroughs in the synthesis of single-atom catalysts (SACs) and their applications in catalytic systems. They have shown excellent activity, selectivity, stability, efficient atom utilization and can serve as an efficient bridge between homogeneous and heterogenous catalysis. Currently, most SACs are synthesized via a bottom-up strategy; however, drawbacks such as the difficulty in accessing high mass activity and controlling homogeneous coordination environments are inevitably encountered, restricting their potential use in the industrial area. In this regard, a novel top-down strategy has been recently developed to fabricate SACs to address these practical issues. The metal loading can be increased to 5% and the coordination environments can also be precisely controlled. This review highlights approaches to the chemical synthesis of SACs towards diverse chemical reactions, especially the recent advances in improving the mass activity and well-defined local structures of SACs. Also, challenges and opportunities for the SACs will be discussed in the later part.

scholarly journals Hydrogen Production from Formic Acid Attained by Bimetallic Heterogeneous PdAg Catalytic Systems

Energies ◽  
2019 ◽  
Vol 12 (21) ◽  
pp. 4027 ◽  
Author(s):  
Miriam Navlani-García ◽  
David Salinas-Torres ◽  
Diego Cazorla-Amorós
Keyword(s):  
Formic Acid ◽  
High Performance ◽  
Heterogeneous Catalysts ◽  
Carbon Materials ◽  
Pd Nanoparticles ◽  
Catalytic Performance ◽  
Catalytic Systems ◽  
Storage Technologies ◽  
The Impact ◽  
Great Focus

The production of H2 from the so-called Liquid Organic Hydrogen Carriers (LOHC) has recently received great focus as an auspicious option to conventional hydrogen storage technologies. Among them, formic acid, the simplest carboxylic acid, has recently emerged as one of the most promising candidates. Catalysts based on Pd nanoparticles are the most fruitfully investigated, and, more specifically, excellent results have been achieved with bimetallic PdAg-based catalytic systems. The enhancement displayed by PdAg catalysts as compared to the monometallic counterpart is ascribed to several effects, such as the formation of electron-rich Pd species or the increased resistance against CO-poisoning. Aside from the features of the metal active phases, the properties of the selected support also play an important role in determining the final catalytic performance. Among them, the use of carbon materials has resulted in great interest by virtue of their outstanding properties and versatility. In the present review, some of the most representative investigations dealing with the design of high-performance PdAg bimetallic heterogeneous catalysts are summarised, paying attention to the impact of the features of the support in the final ability of the catalysts towards the production of H2 from formic acid.

scholarly journals Iodine reduction for reproducible and high-performance perovskite solar cells and modules

2021 ◽  
Vol 7 (10) ◽  
pp. eabe8130
Author(s):  
Shangshang Chen ◽  
Xun Xiao ◽  
Hangyu Gu ◽  
Jinsong Huang
Keyword(s):  
Solar Cells ◽  
High Performance ◽  
High Efficiency ◽  
Electronic Materials ◽  
Substantial Reduction ◽  
Perovskite Solar Cells ◽  
High Yield ◽  
Operation Conditions ◽  
Record Value ◽  
Precursor Powders

Perovskite-based electronic materials and devices such as perovskite solar cells (PSCs) have notoriously bad reproducibility, which greatly impedes both fundamental understanding of their intrinsic properties and real-world applications. Here, we report that organic iodide perovskite precursors can be oxidized to I2 even for carefully sealed precursor powders or solutions, which markedly deteriorates the performance and reproducibility of PSCs. Adding benzylhydrazine hydrochloride (BHC) as a reductant into degraded precursor solutions can effectively reduce the detrimental I2 back to I−, accompanied by a substantial reduction of I3−-induced charge traps in the films. BHC residuals in perovskite films further stabilize the PSCs under operation conditions. BHC improves the stabilized efficiency of the blade-coated p-i-n structure PSCs to a record value of 23.2% (22.62 ± 0.40% certified by National Renewable Energy Laboratory), and the high-efficiency devices have a very high yield. A stabilized aperture efficiency of 18.2% is also achieved on a 35.8-cm2 mini-module.

scholarly journals Catalytic Systems Based on Cp2ZrX2 (X = Cl, H), Organoaluminum Compounds and Perfluorophenylboranes: Role of Zr,Zr- and Zr,Al-Hydride Intermediates in Alkene Dimerization and Oligomerization

Catalysts ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 39
Author(s):  
Lyudmila V. Parfenova ◽  
Pavel V. Kovyazin ◽  
Almira Kh. Bikmeeva ◽  
Eldar R. Palatov
Keyword(s):  
Diffusion Coefficients ◽  
Organoaluminum Compounds ◽  
Zirconium Hydride ◽  
Nmr Studies ◽  
Catalytic Systems ◽  
Selective Formation

The activity and chemoselectivity of the Cp2ZrCl2-XAlBui2 (X = H, Bui) and [Cp2ZrH2]2-ClAlEt2 catalytic systems activated by (Ph3C)[B(C6F5)4] or B(C6F5)3 were studied in reactions with 1-hexene. The activation of the systems by B(C6F5)3 resulted in the selective formation of head-to-tail alkene dimers in up to 93% yields. NMR studies of the reactions of Zr complexes with organoaluminum compounds (OACs) and boron activators showed the formation of Zr,Zr- and Zr,Al-hydride intermediates, for which diffusion coefficients, hydrodynamic radii, and volumes were estimated using the diffusion ordered spectroscopy DOSY. Bis-zirconium hydride clusters of type x[Cp2ZrH2∙Cp2ZrHCl∙ClAlR2]∙yRnAl(C6F5)3−n were found to be the key intermediates of alkene dimerization, whereas cationic Zr,Al-hydrides led to the formation of oligomers.

In situ growth of ultrathin Ni–Fe LDH nanosheets for high performance oxygen evolution reaction

2017 ◽  
Vol 4 (7) ◽  
pp. 1173-1181 ◽  
Author(s):  
Haidong Yang ◽  
Sha Luo ◽  
Yun Bao ◽  
Yutong Luo ◽  
Jun Jin ◽  
...  
Keyword(s):  
Oxygen Evolution ◽  
Oxygen Evolution Reaction ◽  
High Performance ◽  
Copper Foil ◽  
Catalytic Performance ◽  
In Situ Growth ◽  
Ultrathin Nanosheet

The ultrathin Ni70Fe30LDH nanosheets were successfullyin situgrown on anodic polarized copper foil, denoted as u-Ni70Fe30LDHs/a-CF. Benefiting from the ultrathin nanosheet structure, the catalyst exhibits remarkable catalytic performance for OER in 1 M KOH solution.

scholarly journals High-yield production of a super-soluble miniature spidroin for biomimetic high-performance materials

2021 ◽  
Author(s):  
Benjamin Schmuck ◽  
Gabriele Greco ◽  
Andreas Barth ◽  
Nicola M. Pugno ◽  
Jan Johansson ◽  
...  
Keyword(s):  
High Performance ◽  
High Yield ◽  
Yield Production ◽  
High Yield Production

Self-assembled three-dimensional hierarchical graphene hybrid hydrogels with ultrathin β-MnO2 nanobelts for high performance supercapacitors

2015 ◽  
Vol 3 (4) ◽  
pp. 1540-1548 ◽  
Author(s):  
Sheng Zhu ◽  
Hui Zhang ◽  
Ping Chen ◽  
Lin-Hui Nie ◽  
Chuan-Hao Li ◽  
...  
Keyword(s):  
Self Assembly ◽  
High Performance ◽  
Three Dimensional ◽  
The Self ◽  
Mass Loading ◽  
Hybrid Hydrogel ◽  
Precise Control ◽  
Ultrafine Structure ◽  
Hybrid Hydrogels ◽  
Self Assembled

A facile protocol for the self-assembly of the rGO/β-MnO2 hybrid hydrogel with ultrafine structure and precise control of mass-loading for high performance supercapacitors is reported.

Effect of Ions Substitution on Nanospace La-Fe-O Catalytic Properties for Simultaneous Removal of NOx and Soot

2013 ◽  
Vol 740 ◽  
pp. 565-569
Author(s):  
Xiao Xiao Meng ◽  
Mao Xiang Jing ◽  
Feng Lin He ◽  
Xiang Qian Shen
Keyword(s):  
High Performance ◽  
Catalytic Properties ◽  
Catalytic Performance ◽  
Dip Coating ◽  
Exhaust Emission ◽  
Simultaneous Removal ◽  
Microstructural Characteristics ◽  
Coating Method ◽  
Citrate Gel Process ◽  
Dip Coating Method

The catalysts La0.8K0.2FeO3(LKFO), La0.8K0.2Fe0.7Mn0.3O3(LKFMO) and La0.8K0.2Fe0.67Mn0.3Pt0.03O3(LKFMPO) were prepared by the citrate-gel process and the catalyst-coated honeycomb ceramic devices were prepared by the citrate-gel assisted dip-coating method. All the catalysts have a high performance on the simultaneous removal of NOxand soot at a temperature range of 200 to 400°C under the practical diesel exhaust emission. The obvious catalytic improvement is largely due to the effects of ions substitution, pore structure and microstructural characteristics of the catalysts. The catalytic performance order is LKFMPO > LKFMO > LKFO. Among them the LKFMPO catalyst shows the best catalytic properties, especially in the removal of NOx, with a maximum conversion rate of NOx(21.2%).

scholarly journals Effect of Fe Additives on the Catalytic Performance of Ion-Exchanged CsX Zeolites for Side-Chain Alkylation of Toluene with Methanol

Catalysts ◽  
2019 ◽  
Vol 9 (10) ◽  
pp. 829 ◽  
Author(s):  
Zhang ◽  
Yuan ◽  
Miao ◽  
Li ◽  
Shan ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Catalytic Performance ◽  
High Yield ◽  
Side Chain ◽  
Impregnation Method ◽  
Basic Sites ◽  
Lewis Acidic Sites ◽  
X Zeolite ◽  
Acidic Sites ◽  
Negative Effect

The side-chain alkylation of toluene with methanol was investigated over some Fe-modified Cs ion-exchanged X zeolite (CsX) catalysts prepared via the impregnation method using different iron sources. The absorption/activation behaviors of the reactants on the surface of the catalysts were studied by in situ Fourier-transform infrared (FT-IR) spectroscopy and temperature programmed desorption (TPD) mass measurements. Modification of CsX with a small amount of FeCl3 could result in a considerable decrease in catalytic activity, due mainly to the remarkable decrease in the density of acidic and basic sites of the catalysts. Interestingly, the Fe(NO3)3-modified CsX with an optimum Fe loading of 0.15 wt.% shows improved catalytic activity and high yield compared to the side-chain alkylation products. Modification of CsX with Fe(NO3)3 could also result in a decrease in basic sites of the catalyst. However, such a change does not bring an obvious negative effect on the adsorption/activation of toluene, while it could effectively inhibit the generation of the undesired bidentate formate. Furthermore, the introduced FeOx species (derived from the decomposition of Fe(NO3)3) may also act as new Lewis acidic sites to participate in the activation of methanol and to stabilize the formed active intermediates (i.e., unidentate formate). Therefore, modification of CsX with a suitable amount of Fe(NO3)3 may adjust its adsorption/activation ability for reagents by changing the acid–base properties of the catalyst, which can finally enhance the catalytic performance for the side-chain alkylation of toluene with methanol.

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