Achieving super dispersed metallic nickel nanoparticles over MCM-41 for highly active and stable hydrogenation of olefins and aromatics

Zhang, Jiaxiang; Wang, Tianzuo; Shi, Chengxiang; Pan, Lun; Zhang, Xiangwen; Peng, Chong; Zou, Ji‐Jun

doi:10.1016/j.cej.2023.144197

Cited by 11 publications

(4 citation statements)

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“…From Figure f, the negative electron density for Ni indicates that the In–Ni bond in InNi 3 (201) is polarized, resulting in the transfer of electrons from In to Ni atoms, which is in agreement with the results of XPS. It has been reported in previous studies that CO* is negatively charged and the CO adsorption is weakened due to repulsion with the negatively charged metal Ni, leading to a change in the hydrogenation product …”

Section: Resultsmentioning

confidence: 97%

Tuning the CO₂ Hydrogenation Activity and Selectivity by Highly Dispersed Ni–In Intermetallic Alloy Compounds

Zhang,

Li,

Xiao

et al. 2023

ACS Sustainable Chem. Eng.

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Reverse water−gas shift (RWGS) reaction is considered as an effective solution for conversion of greenhouse gas of the CO 2 to CO, but it still suffers from relatively low activity and selectivity at low temperatures. Herein, we report the catalytic performance and mechanism of NiIn x /SBA-15 with different Ni and In (indium) molar ratios for the RWGS reaction at a low temperature. The results showed that the increment of the In/Ni ratio in intermetallic alloy compounds (IMCs) inhibits CO* adsorption through the "active site isolation" effect, thus improving selectivity of CO. In terms of In−Ni IMCs, Ni acts as the active center but is isolated by In atoms for the CO 2 hydrogenation reaction. XRD and HRTEM showed that Ni and In formed the IMC and were highly dispersed on the large surface area of SBA-15. It was also demonstrated by H 2 -TPR that the addition of In enhanced the interaction between Ni and the support, thus improving the stability of the catalyst with good anti-sintering. Meanwhile, the aggregation charge density of Ni was obtained by In additives, as verified by XPS and DFT simulation. After optimizing the In/Ni molar ratio, the NiIn 0.5 /SBA-15 exhibited a CO 2 conversion of 29% at 400 °C, 0.1 MPa, and 24,000 mL/g cat •h, with a CO selectivity of over 99% and a production rate of about 47 mmol/g cat •h, which is superior to those of the most reported nickel-based catalysts. At the same time, NiIn 0.5 /SBA-15 showed good long-time stability and the conversion of CO 2 was maintained well after a 25 h reaction. In situ DRIFTS reveals a change for surface intermediates from HCOO* to COOH* during CO 2 activation after the introduction of In, leading to a rapid desorption of CO and avoiding further hydrogenation to form CH 4 , which can also be demonstrated by CO-TPD. The highly dispersed Ni−In IMCs with weak adsorption capacity of CO are the main reason for achieving high activity and selectivity for RWGS at low temperatures.

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Section: Resultsmentioning

confidence: 97%

Tuning the CO₂ Hydrogenation Activity and Selectivity by Highly Dispersed Ni–In Intermetallic Alloy Compounds

Zhang,

Li,

Xiao

et al. 2023

ACS Sustainable Chem. Eng.

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“…The effect of the Ni loading amount was studied on the Ni/MgO catalyst. Excessive reduction temperatures are recognized to induce the sintering of Ni nanoparticles. , Therefore, the catalysts with different Ni loadings are reduced under a hydrogen atmosphere at 500 °C. The HDO activities of the as-prepared catalysts and product distributions are shown in Figure b and Table S2.…”

Section: Resultsmentioning

confidence: 99%

Water Splitting Integrated with Self-Transfer Hydrogenolysis for Efficient Demethoxylation of Guaiacols to Phenols over the Ni/MgO Catalyst

Ren,

Qiang,

Sun

et al. 2024

ACS Catal.

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This work demonstrates the upgrading of ligninderived monomers through a cascade demethoxylation, aqueousphase reforming reaction, eliminating the need for external hydrogen supply. The core of this research lies in the use of neat water as both reaction medium and the hydrogen donor over a multifunctional Ni/MgO catalyst, which is responsible for water splitting, aqueous-phase reforming of in situ generated methanol, and selective cleavage of the C−O bond, finally establishing an efficient one-pot approach achieving a high yield of phenols. Reaction mechanism studies proved that the initial H* source came from water by its splitting on the surface of the Ni/MgO catalyst, which triggered the fracture of the aromatic ether bond to afford phenols and CH 3 O*. The subsequent aqueous-phase reforming of CH 3 O* and OH* generated more hydrogen and further accelerated the hydrodeoxygenation (HDO) process. A high conversion of 87.8% with a selectivity of 88.9% for phenol could be achieved at 190 °C from guaiacol. Thanks to the interesting water-splitting mechanisms and strong metal−support interaction (SMSI), Ni/MgO exhibited significantly enhanced stability compared to the previously reported nanoporous Ni catalysts. Further, with real lignin as the substrate, 16.3 wt % combined yield of phenol and 4methylphenol could be acquired under optimized conditions. Overall, this "H 2 -free" approach offers a promising alternative to conventional biorefinery processes, addressing the challenges of hydrogen sourcing and economic feasibility.

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“…When the reaction temperature is stabilized at the setting value, hydrogen gas is introduced to reach the target pressure. During the reaction, the catalyst undergoes in situ reduction in the autoclave at a certain reaction temperature and hydrogen pressure, where Ni 2+ on the catalyst surface is partially reduced to zerovalent Ni, which gives it hydrogenation activity . As the activation time required for the catalyst varies at different temperatures, the reaction time at which the reaction starts is recorded as 0.…”

Section: Methodsmentioning

confidence: 99%

Intrinsic Kinetics of Dibenzyltoluene Hydrogenation over a Supported Ni Catalyst for Green Hydrogen Storage

Li,

Zhang,

Zhang

et al. 2023

Ind. Eng. Chem. Res.

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As an effective initiative to avoid the fluctuation of renewable energy sources, hydrogen energy storage technology is an important link between hydrogen production and utilization, where liquid organic hydrogen carriers (LOHCs) offer the advantages of high hydrogen storage density and available storage conditions. Dibenzyltoluene (DBT) is a promising LOHC, but the hydrogenation reaction pathways and kinetic parameters guiding reactor design and catalyst performance evaluation are not clear. Here, we systematically investigated the kinetics of DBT hydrogenation over a commercial Ni/Al 2 O 3 catalyst. DBT hydrogenation reaction follows a two-step series reaction from DBT to 12H-DBT and another one-step reaction from 12H-DBT to 18H-DBT. Increasing the hydrogen pressure and temperature can improve the reaction rate, while the stirring speed has no obvious influence. The reaction order for each hydrogenation step (i.e., DBT to 6H-DBT, 6H-DBT to 12H-DBT, and 12H-DBT to 18H-DBT) approximates 1 with respect to reactant concentration (1.06, 0.976, and 1.36, respectively), whereas the reaction order with respect to H 2 pressure is approximately equal (0.79, 0.74, 0.745, respectively). The activation energies of each step are 59.254, 56.061, and 64.641 kJ•mol −1 , respectively, revealing that 12H-DBT hydrogenation is the rate-determining step. This work is expected to provide a new understanding of the nature of DBT hydrogenation reactions, which is meaningful for the evaluation of catalyst performance and for reactor design.

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Achieving super dispersed metallic nickel nanoparticles over MCM-41 for highly active and stable hydrogenation of olefins and aromatics

Cited by 11 publications

References 50 publications

Tuning the CO₂ Hydrogenation Activity and Selectivity by Highly Dispersed Ni–In Intermetallic Alloy Compounds

Tuning the CO₂ Hydrogenation Activity and Selectivity by Highly Dispersed Ni–In Intermetallic Alloy Compounds

Water Splitting Integrated with Self-Transfer Hydrogenolysis for Efficient Demethoxylation of Guaiacols to Phenols over the Ni/MgO Catalyst

Intrinsic Kinetics of Dibenzyltoluene Hydrogenation over a Supported Ni Catalyst for Green Hydrogen Storage

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Achieving super dispersed metallic nickel nanoparticles over MCM-41 for highly active and stable hydrogenation of olefins and aromatics

Cited by 11 publications

References 50 publications

Tuning the CO2 Hydrogenation Activity and Selectivity by Highly Dispersed Ni–In Intermetallic Alloy Compounds

Tuning the CO2 Hydrogenation Activity and Selectivity by Highly Dispersed Ni–In Intermetallic Alloy Compounds

Water Splitting Integrated with Self-Transfer Hydrogenolysis for Efficient Demethoxylation of Guaiacols to Phenols over the Ni/MgO Catalyst

Intrinsic Kinetics of Dibenzyltoluene Hydrogenation over a Supported Ni Catalyst for Green Hydrogen Storage

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Tuning the CO₂ Hydrogenation Activity and Selectivity by Highly Dispersed Ni–In Intermetallic Alloy Compounds

Tuning the CO₂ Hydrogenation Activity and Selectivity by Highly Dispersed Ni–In Intermetallic Alloy Compounds