Dry Reforming of Methane (DRM) by Highly Active and Stable Ni Nanoparticles on Renewable Porous Carbons

In this study, Ni nanoparticles supported on renewable porous carbon were prepared using hydrochar as a carbon precursor via in situ formation and self-reduction. The structure properties of the prepared nanocatalysts were characterized by multiple techniques, including XRD, SEM, and HR-TEM, and the dry reforming of methane (DRM) performance of the nanocatalysts in terms of conversion efficiency and reactivity stability was evaluated. The results revealed that the Ni2+ was uniformly anchored on the surface of the hydrochar, and subsequently the Ni nanoparticles were well dispersed in the composite with a diameter of less than 8 nm and had a narrow particle size distribution at a temperature lower than 800 °C. With an increased temperature from 800 to 900 °C, the significant sintering and agglomeration of nickel particles and the transformation from amorphous carbon to graphitic structure were observed in the composite. The nanocatalysts prepared at a temperature of 700 °C (Ni@C-700) and 800 °C (Ni@C-800) exhibited a high reforming conversion rate and catalytic stability of CH4 by CO2 (around 52% for Ni@C-700 and 70% for Ni@C-800 after 800 min of run-time, respectively). As for the composite obtained at 900 (Ni@C-900), the highly graphitic degree was coupled with the significantly increased nickel particle size, and this resulted in a remarkably decreased conversion efficiency. The present study offers a valuable application of the hydrochar and a facile and green approach to prepare highly active and cost-efficient Ni nanoparticles on porous carbons towards the dry reforming of methane.

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Novel synthesis of a NiMoP phosphide catalyst via carbothermal reduction for dry reforming of methane

Catalysis Science & Technology ◽

10.1039/d1cy01434j ◽

2021 ◽

Author(s):

Xinyu Chen ◽

Wei Ding ◽

Zhiwei Yao ◽

Na Sun ◽

Zhimeng Wang ◽

...

Keyword(s):

Particle Size ◽

Carbon Content ◽

Carbothermal Reduction ◽

Average Particle Size ◽

Dry Reforming ◽

Dry Reforming Of Methane ◽

Average Particle ◽

Novel Synthesis ◽

Highly Dispersed

A Highly dispersed NiMoP phosphide catalyst with an average particle size of 9.1 nm and a carbon content of 53.5 wt% was firstly synthesized by carbothermal route using glucose as...

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Atomically dispersed nickel as coke-resistant active sites for methane dry reforming

Nature Communications ◽

10.1038/s41467-019-12843-w ◽

2019 ◽

Vol 10 (1) ◽

Cited By ~ 46

Author(s):

Mohcin Akri ◽

Shu Zhao ◽

Xiaoyu Li ◽

Ketao Zang ◽

Adam F. Lee ◽

...

Keyword(s):

Active Sites ◽

Large Scale ◽

Low Cost ◽

Coke Formation ◽

Dry Reforming ◽

Dry Reforming Of Methane ◽

Highly Active ◽

Catalytic Sites ◽

Earth Abundant ◽

Poor Stability

AbstractDry reforming of methane (DRM) is an attractive route to utilize CO2 as a chemical feedstock with which to convert CH4 into valuable syngas and simultaneously mitigate both greenhouse gases. Ni-based DRM catalysts are promising due to their high activity and low cost, but suffer from poor stability due to coke formation which has hindered their commercialization. Herein, we report that atomically dispersed Ni single atoms, stabilized by interaction with Ce-doped hydroxyapatite, are highly active and coke-resistant catalytic sites for DRM. Experimental and computational studies reveal that isolated Ni atoms are intrinsically coke-resistant due to their unique ability to only activate the first C-H bond in CH4, thus avoiding methane deep decomposition into carbon. This discovery offers new opportunities to develop large-scale DRM processes using earth abundant catalysts.

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Highly Dispersed Ni Nanoparticles on Anhydrous Calcium Silicate (ACS) Nanosheets for Catalytic Dry Reforming of Methane: Tuning the Activity by Different Ways of Ni Introduction

Chemistry - An Asian Journal ◽

10.1002/asia.201900611 ◽

2019 ◽

Author(s):

Kefa Sheng ◽

Fang Zeng ◽

Fei Pang ◽

Jianping Ge

Keyword(s):

Calcium Silicate ◽

Dry Reforming ◽

Dry Reforming Of Methane ◽

Ni Nanoparticles ◽

Highly Dispersed

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Highly active and stable Ni dispersed on mesoporous CeO2-Al2O3 catalysts for production of syngas by dry reforming of methane

Applied Catalysis B Environmental ◽

10.1016/j.apcatb.2020.119459 ◽

2021 ◽

Vol 281 ◽

pp. 119459 ◽

Cited By ~ 3

Author(s):

André L.A. Marinho ◽

Fabio S. Toniolo ◽

Fabio B. Noronha ◽

Florence Epron ◽

Daniel Duprez ◽

...

Keyword(s):

Dry Reforming ◽

Dry Reforming Of Methane ◽

Highly Active ◽

Mesoporous Ceo2

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Embedded Ni nanoparticles in CeZrO2 as stable catalyst for dry reforming of methane

Applied Catalysis B Environmental ◽

10.1016/j.apcatb.2019.118387 ◽

2020 ◽

Vol 268 ◽

pp. 118387 ◽

Cited By ~ 12

Author(s):

André L.A. Marinho ◽

Raimundo C. Rabelo-Neto ◽

Florence Epron ◽

Nicolas Bion ◽

Fabio S. Toniolo ◽

...

Keyword(s):

Dry Reforming ◽

Dry Reforming Of Methane ◽

Ni Nanoparticles ◽

Stable Catalyst

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Scalable Production of Carbon Encapsulated Ni Nanoparticles by Water Arc Discharge: Structural and Magnetic Properties

Journal of Metastable and Nanocrystalline Materials ◽

10.4028/www.scientific.net/jmnm.23.87 ◽

2005 ◽

Vol 23 ◽

pp. 87-90 ◽

Cited By ~ 1

Author(s):

K.H. Ang ◽

I. Alexandrou ◽

N.D. Mathur ◽

R. Lacerda ◽

I.Y.Y. Bu ◽

...

Keyword(s):

Particle Size ◽

Magnetic Properties ◽

Particle Size Distribution ◽

Size Distribution ◽

Arc Discharge ◽

Narrow Particle Size Distribution ◽

Ni Nanoparticles ◽

X Ray Diffraction ◽

Transmission Electron ◽

Water Container

An electric arc discharge in de-ionised water between a solid graphite cathode and an anode made by compressing Ni and C containing powders in a mass ratio of Ni:C = 7:3 was used here to prepare carbon encapsulated Ni nanoparticles in the form of powder suspended in water. The morphology of the produced material was analysed using high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). The magnetic properties of the samples were determined using a Princeton vibrating sample magnetometer (VSM). Collection of the powder produced from different depths in the water container has proved to be an effective method for obtaining samples with narrow particle size distribution. Further material purification by dry NH4 plasma etching was used to remove the amorphous carbon content of the samples. XRD and HRTEM analysis showed that the material synthesized is fcc Ni particles with mean particle size ranging from 14 to 30 nm encapsulated in 2 to 5 graphitic cages. The data suggests that the process reported has the ability to mass-produce carbon encapsulated ferromagnetic nanoparticles with desired particle size distribution, and hence with controlled size-dependent magnetic properties.

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In situ preparation of Ni nanoparticles in cerium-modified silica aerogels for coking- and sintering-resistant dry reforming of methane

New Journal of Chemistry ◽

10.1039/c7nj00115k ◽

2017 ◽

Vol 41 (12) ◽

pp. 4869-4878 ◽

Cited By ~ 29

Author(s):

Xiaoyuan Zhao ◽

Meirong Lu ◽

Hongrui Li ◽

Jianhui Fang ◽

Liyi Shi ◽

...

Keyword(s):

Silica Aerogels ◽

Dry Reforming ◽

Dry Reforming Of Methane ◽

Ni Nanoparticles ◽

Modified Silica ◽

In Situ Preparation

Ni nanoparticles in nanochannels of cerium-modified silica aerogels were in situ prepared for coking-resistant dry reforming of methane.

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Encapsulated Ni@La2O3/SiO2 Catalyst with a One-Pot Method for the Dry Reforming of Methane

Catalysts ◽

10.3390/catal10010038 ◽

2019 ◽

Vol 10 (1) ◽

pp. 38 ◽

Cited By ~ 4

Author(s):

Luhui Wang ◽

Rong Hu ◽

Hui Liu ◽

Qinhong Wei ◽

Dandan Gong ◽

...

Keyword(s):

Carbon Deposition ◽

Synthesis Method ◽

Space Velocity ◽

Dry Reforming ◽

Dry Reforming Of Methane ◽

Catalyst Characterization ◽

Porous System ◽

Ni Nanoparticles ◽

Solution Combustion ◽

One Pot

Ni nanoparticles encapsulated within La2O3 porous system (Ni@La2O3), the latter supported on SiO2 (Ni@La2O3)/SiO2), effectively inhibit carbon deposition for the dry reforming of methane. In this study, Ni@La2O3/SiO2 catalyst was prepared using a one-pot colloidal solution combustion method. Catalyst characterization demonstrates that the amorphous La2O3 layer was coated on SiO2, and small Ni nanoparticles were encapsulated within the layer of amorphous La2O3. During 50 h of dry reforming of methane at 700 °C and using a weight hourly space velocity (WHSV) of 120,000 mL gcat−1 h−1, the CH4 conversion obtained was maintained at 80%, which is near the equilibrium value, while that of impregnated Ni–La2O3/SiO2 catalyst decreased from 63% to 49%. The Ni@La2O3/SiO2 catalyst exhibited very good resistance to carbon deposition, and only 1.6 wt% carbon was formed on the Ni@La2O3/SiO2 catalyst after 50 h of reaction, far lower than that of 11.5 wt% deposited on the Ni–La2O3/SiO2 catalyst. This was mainly attributed to the encapsulated Ni nanoparticles in the amorphous La2O3 layer. In addition, after reaction at 700 °C for 80 h with a high WHSV of 600,000 mL gcat−1 h−1, the Ni@La2O3/SiO2 catalyst exhibited high CH4 conversion rate, ca. 10.10 mmol gNi−1 s−1. These findings outline a simple synthesis method to prepare supported encapsulated Ni within a metal oxide porous structure catalyst for the dry reforming of methane reaction.

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