Ni-doped Catalysts Research Articles

Co3O4-Based Materials as Potential Catalysts for Methane Detection in Catalytic Gas Sensors.

The present work deals with the development of Co3O4-based catalysts for potential application in catalytic gas sensors for methane (CH4) detection. Among the transition-metal oxide catalysts, Co3O4 exhibits the highest activity in catalytic combustion. Doping Co3O4 with another metal can further improve its catalytic performance. Despite their promising properties, Co3O4 materials have rarely been tested for use in catalytic gas sensors. In our study, the influence of catalyst morphology and Ni doping on the catalytic activity and thermal stability of Co3O4-based catalysts was analyzed by differential calorimetry by measuring the thermal response to 1% CH4. The morphology of two Co3O4 catalysts and two NixCo3-xO4 with a Ni:Co molar ratio of 1:2 and 1:5 was studied using scanning transmission electron microscopy and energy dispersive X-ray analysis. The catalysts were synthesized by (co)precipitation with KOH solution. The investigations showed that Ni doping can improve the catalytic activity of Co3O4 catalysts. The thermal response of Ni-doped catalysts was increased by more than 20% at 400 °C and 450 °C compared to one of the studied Co3O4 oxides. However, the thermal response of the other Co3O4 was even higher than that of NixCo3-xO4 catalysts (8% at 400 °C). Furthermore, the modification of Co3O4 with Ni simultaneously brings stability problems at higher operating temperatures (≥400 °C) due to the observed inhomogeneous Ni distribution in the structure of NixCo3-xO4. In particular, the NixCo3-xO4 with high Ni content (Ni:Co ratio 1:2) showed apparent NiO separation and thus a strong decrease in thermal response of 8% after 24 h of heat treatment at 400 °C. The reaction of the Co3O4 catalysts remained quite stable. Therefore, controlling the structure and morphology of Co3O4 achieved more promising results, demonstrating its applicability as a catalyst for gas sensing.

Metal doped TiO2 decorated carbon nanostructured materials as an emerging photocatalysts for solar fuels production

The concept of photocatalytic CO2 and H2O conversion to solar fuels and value-added products provides simultaneous solution for increased energy demands and environmental problems. However, the lack of efficient photocatalysts restrains the large-scale development of photocatalytic technology. In the present study, noble (Pt and Au) and transition metal (Ni) doped nanoflakes assembled on TiO2@carbon microrods with high surface area and rutile crystal structure is prepared via fast, versatile solvothermal method. The photocatalytic performance of the prepared nanocomposites was evaluated in two photocatalytic systems: CO2 reduction and hydrogen production via photoreforming. Pt-doped catalyst showed enhanced hydrogen production efficiency and increased CH4 selectivity, while Ni-doped catalyst exhibited remarkable CO2 reduction activity with higher selectivity towards CO. The mechanism of Pt-promoted CH4 formation and Ni- and Au-promoted CO formation was thoroughly discussed regarding kinetic and thermodynamic parameters.

Stability, deactivation and regeneration study of a newly developed HZSM-5 and Ni-doped HZSM-5 zeolite catalysts for ethanol-to-hydrocarbon conversion

This work investigates the stability and regeneration of HZSM-5 and Ni/HZSM-5 catalysts in the ethanol-to-hydrocarbon conversion. The catalysts were characterised using different techniques and evaluated at 623 K and 7 h−1 for 96 h TOS with two regeneration cycles. HZSM-5 showed high stability with 100% ethanol conversion, while Ni/HZSM-5 catalysts maintained 100% stability for 48 h before dropping. Regenerated catalysts were comparable to the originals in terms of product distribution, stability, and performance. HZSM-5 preferred BTX, while Ni-doped catalysts favoured C5-C8, C9-C12, and C12+ synthesis. The regeneration process restored catalytic activity, especially for the Ni-doped catalysts, extending their life and reducing replacement costs.

Synergistic Activation of Inert Iron Oxide Basal Planes through Heterostructure Formation and Doping for Efficient Hydrogen Evolution.

Iron oxides have emerged as a very promising and cost-effective alternative to precious metal catalysts for hydrogen production. However, the inert basal plane of iron oxides needs to be activated to enhance their catalytic efficiency. In this study, we employed heterostructure engineering and doped nickel to cooperatively activate the basal planes of iron oxide (Ni-Fe2 O3 /CeO2 HSs) to achieve high hydrogen evolution reaction (HER) activity. The Ni-Fe2 O3 /CeO2 HSs electrocatalyst demonstrates excellent basic HER activity and stability, such as an extremely low overpotential of 43 mV at 10 mA cm-2 current density and corresponding Tafel slope of 58.6 mV dec-1 . The increase in electrocatalyst activity and acceleration of hydrogen precipitation kinetics arises from the dual modulation of Ni doping and heterostructure, which not only modulates the electrocatalyst's electronic structure, but also increases the number and exposure of active sites. Remarkably, the generation of heterogeneous structure makes the catalyst se. The Ni-doped catalyst has not only increased HER activity but also low-temperature resistance. These results suggest that the synergistic activation of inert iron oxide basal planes through heterostructure formation and doping is a feasible strategy. Furthermore, for efficient electrocatalytic water splitting, this technique can be extended to other non-noble metal oxides.

Development of porous MIL-101 derived catalyst application for green diesel production

A novel three-dimensional MIL-101 derived porous carbon-based Ni-doped catalyst was synthesised via slow pyrolysis of Ni/MIL-101(Cr) precursor at 600 °C for 4 h. The catalytic activities were evaluated via one-pot hydrodeoxygenation (HDO) reactions by using palmitic acid (PA) as a model compound to produce green diesel within the range of a paraffinic hydrocarbon. The results show that Ni/P-MIL-101 exhibited excellent catalytic activity and recyclability in the HDO reaction of PA at a reaction temperature of 400 °C for 3 h under 3 MPa purified H2 pressure with 5 wt% catalyst loading. The conversion of PA and hydrocarbon selectivity were found to be 100 % with Ni loading > 8 wt% on P-MIL-101. In addition, both 25 and 14 wt% Ni/P-MIL-101 catalysts were able to recycle up to 7 and 15 times, respectively, and nearly 100 % alkane yield was achieved. The unique properties of Ni/P-MIL-101 catalyst such as finely dispersed added Ni, abundant acid and basic sites, and the presence of Cr2O3 active sites from pyrolysed MIL-101 with its mesoporous structures play a synergetic role in obtaining a very efficient catalyst for hydrodeoxygenation reaction. It is worth mentioning that the catalyst has an excellent catalytic effect on different kinds of fatty acid (ester) raw materials. Therefore, this Ni/P-MIL-101 catalyst has good prospects and potential for industrial application in green diesel production.

Promotion effect of Ni doping on the oxygen resistance property of Fe/CeO2 catalyst for CO-SCR reaction: Activity test and mechanism investigation

Catalytic reduction of NO using CO, which is usually present in the flue gas of the iron and steel industry, is considered as an economical and eco-friendly de-NOx method (CO-SCR). However, the oxygen present in the flue gas will significantly inhibit the CO-SCR activity of the catalyst, thereby limiting its industrial application. Herein, catalysts based on iron and cerium oxides were prepared and modified with different metals to investigate their performance for the CO-SCR reaction in the presence of oxygen. The results show that the Fe/CeO2 catalyst can reach 99% NO conversion at 200 °C, but its activity decreased dramatically to 42.7% when the oxygen is present (0.5 vol%). By contrast, the NO conversion of Ni-doped Fe/CeO2 catalyst demonstrated significant enhanced oxygen resistance and could achieve 92% even at 150 °C in the presence of 0.5 vol% oxygen. Characterization techniques such as N2 adsorption, XRD, SEM/TEM, XPS, H2-TPR, and in situ DRIFT were employed to investigate the mechanism of the improved oxygen resistance property of Ni-doped catalyst. The results show that the doped Ni can interact with Fe species, increases the BET surface area of the catalyst and generates more surface oxygen vacancies (SOV) and surface synergetic oxygen vacancy (SSOV) in CO-SCR reaction, thereby improving the redox performance of the catalyst. In situ DRIFT results show that the better redox performance of NiFe/CeO2 catalyst is conducive to the conversion of adsorbed NOx species to the reactive intermediate NO2- species during the reaction. Meanwhile, the enhanced SOV/SSOV in the NiFe/CeO2 catalyst can remain active in the presence of oxygen. Therefore, the NiFe/CeO2 catalyst exhibits a promising catalytic activity in CO-SCR reaction when oxygen is present.

Structural Characterization of Nickel-Doped Aluminum Oxide Cations by Cryogenic Ion Trap Vibrational Spectroscopy.

Isolated nickel-doped aluminum oxide cations (NiOm)(Al2O3)n(AlO)+ with m = 1-2 and n = 1-3 are investigated by infrared photodissociation (IRPD) spectroscopy in combination with density functional theory and the single-component artificial force-induced reaction method. IRPD spectra of the corresponding He-tagged cations are reported in the 400-1200 cm-1 spectral range and assigned based on a comparison to calculated harmonic IR spectra of low-energy isomers. Simulated spectra of the lowest energy structures generally match the experimental spectra, but multiple isomers may contribute to the spectra of the m = 2 series. The identified structures of the oxides (m = 1) correspond to inserting a Ni-O moiety into an Al-O bond of the corresponding (Al2O3)1-3(AlO)+ cluster, yielding either a doubly or triply coordinated Ni2+ center. The m = 2 clusters prefer similar structures in which the additional O atom either is incorporated into a peroxide unit, leaving the oxidation state of the Ni2+ atom unchanged, or forms a biradical comprising a terminal oxygen radical anion Al-O•- and a Ni3+ species. These clusters represent model systems for under-coordinated Ni sites in alumina-supported Ni catalysts and should prove helpful in disentangling the mechanism of selective oxidative dehydrogenation of alkanes by Ni-doped catalysts.

Ni–Mg–Al Catalysts Effectively Promote Depolymerization of Rice Husk Lignin to Bio-Oil

Catalytic depolymerization of lignin to produce bio-oil, liquid fuels, and aromatic chemicals in high yields is important for a biorefinery to remain competitive. In this study, undoped and Ni-doped catalysts for depolymerization of rice husk lignin (RHL) were developed and analyzed. The results showed that the catalysts had hydrotalcite-like structures with lamellar morphology. With suitable Ni-doping amount, the catalysts had high activity, thus better promoted the depolymerization of RHL. Among all catalysts, the Ni1/4MgAl catalyst could best promote the cleavage of the β-O-4 aryl ether bond in RHL molecule and thus could substantially increase the yields of bio-oil. The depolymerization catalyzed by this catalyst was also found to be temperature-, time-, and solvent-dependent. This study provides information that can be beneficial to the biorefinery industries and may help promote the valorization of lignin.

Highly Efficient Ni-Doped Iron Catalyst for Ammonia Synthesis from Quantum-Mechanics-Based Hierarchical High-Throughput Catalyst Screening

To discover more efficient industrial catalysts for ammonia synthesis via the Haber–Bosch (HB) process, we employed quantum mechanics (QM)-based hierarchical high-throughput catalyst screening (HHTCS) to test a wide group of elements (34) as candidates to dope the Fe(111) catalyst subsurface. The QM free-energy reaction network of HB over Fe(111) yields ten barriers as potentially rate-determining, of which we select four as prototypical, arrange them hierarchically, and define a corresponding set of screening criteria, which we then use to screen candidate catalysts. This leads to two promising candidates (Co and Ni), from which we selected the most promising (Ni) for a complete QM and kinetic study. The kinetic Monte Carlo (kMC) simulations predict a 16-fold increase in HB turn-over frequency (TOF) for the Ni-doped catalyst compared to the pure Fe(111) surface under realistic conditions. The 16-fold increase in HB TOF is a significant improvement and may trigger future experimental studies to validate our prediction. This TOF improvement could lead to similar reaction rates as with pure Fe but at a reaction temperature decreased by 100° from 773 to 673 K and a total reactant pressure decreased by 6 times from 201 to 34 atm. We interpret the reasons underlying this improvement using valence bond and kinetic analyses. We suggest this Ni-doped Fe(111) catalyst as a candidate to reduce the world energy consumption for the HB process while satisfying future needs for energy and environment.

Catalytic pyrolysis over transition metal-modified zeolites: A comparative study between catalyst activity and deactivation

Using metal-doped zeolites in catalytic pyrolysis of biomass is a well-known approach to promote the formation of certain compounds. One of the major technical issues with such catalysts is their rapid deactivation due to coke formation. However, little is known about how metal-doping influences the characteristics of coking, such as coking rate and its composition.In this study, four different materials were experimentally evaluated based on their catalytic activity and coking characteristics: HZSM-5, Fe/ZSM-5, Ni/ZSM-5 and FeNi/ZSM-5. The materials were prepared and characterized followed by screening in a bench-scale setup for in-situ catalytic pyrolysis. The mass balance and composition of pyrolysis products including catalyst coke were analyzed.It was found that metal-doping increases the concentration of aromatic hydrocarbons in the liquid product from 59.0 to 82.8% of GC/MS peak area, especially monoaromatic hydrocarbons (MAHs) and naphthalenes. Fe mainly increases the selectivity of MAHs whereas Ni additionally promotes naphthalenes. FeNi/ZSM-5 reflects the combined effect of Fe- and Ni-doped catalysts. Regarding the catalyst coke composition, metal-doped catalysts present an increased concentration of aromatic hydrocarbons. For each catalyst, the chemical composition of the coke reflects the catalytic activity seen in vapor upgrading. Based on the findings in this work, a reaction pathway for metal-doped ZSM-5 and HZSM-5 is proposed.The results also show that metal-doping increases the formation of catalyst coke, mainly due to a higher concentration of strong acid sites. Also, the severity of coking was found to be dependent on the strength of acid sites. The coke yield increased from 3.5 wt% in the case of HZSM-5 to maximum 7.2 wt% over Fe/ZSM-5. At the same time metal-doping reduces the temperature of catalyst regeneration and catalyzes the oxidation of coke. Overall, this work presents a comparative study between catalyst activity and deactivation during thermochemical conversion of biomass.

Study of Methane Decomposition on Fe/MgO-Based Catalyst Modified by Ni, Co, and Mn Additives

Catalytic decomposition of methane (CDM) generates clean hydrogen and carbon nanomaterials. In this study, methane decomposition to hydrogen and carbon was investigated over Ni-, Co-, or Mn-doped Fe/MgO catalysts. The doping effect of different metals, varying from 3 to 10 wt%, was investigated. The catalytic performance of the obtained materials (noted 15%Fe+x%metal/MgO) revealed that the doping effect of Ni, Co, and Mn significantly improved the activity of Fe/MgO. Among the Ni-doped catalyst series, the 15%Fe+3%Ni/MgO catalyst performed better than the rest of the Ni catalysts. The 6%Co-containing catalyst remained the best in terms of activity in the Co-doped catalyst series and the 15%Fe+6%Mn/MgO solid showed better methane conversion for the Mn-doped series. Overall, 3%Ni-containing catalyst displayed the best catalytic performance among all Ni-, Co-, and Mn-doped catalysts. XRD, N2 sorption, and H2 temperature-programmed reduction (TPR), Laser–Raman spectroscopy, thermogravimetric analysis (TGA) under air, and temperature-programmed oxidation (TPO) were used for catalyst characterization. The results revealed that all the doped catalysts exhibited better metallic active site distribution than 15%Fe/MgO and proved that metal doping played a crucial role in catalytic performance.

Influence of electronic effect on methane catalytic combustion over PdNi/Al2O3

A series of PdNi/Al2O3 catalysts with different compositions was prepared by co-reduction method. The influence of Ni amount on the catalytic combustion of methane was studied. X-ray diffractometry and X-ray photo-electron spectroscopy were employed to characterize the dispersion and electronic state of the active phase. Temperature-programmed oxidation was carried out to study the thermal stability affected by Ni doping. It has been demonstrated that Ni addition changed particle size and oxidation state of PdO (x) . The results indicate that the promotion of Ni to the Pd/Al2O3 resulted from both size effect and electronic effect. In addition, the thermal stability of the Ni-doped catalysts were enhanced.

Stability Enhancement in Ni-Promoted Cu−Fe Spinel Catalysts for Dimethyl Ether Steam Reforming

Effects of Ni doping on the catalytic behavior of CuxNi1−xFe2O4 (x = 1, 0.95, 0.90, 0.50) mixed with Al2O3 were investigated in steam reforming of dimethyl ether for hydrogen production. The stability of the catalyst was significantly enhanced by doping Ni species to CuFe2O4. Formation of CuNi alloy was confirmed as the amount of Ni addition increased. The suppression of the sintering rate was clearly evidenced over Ni-doped catalysts as compared with the undoped one, while the effect on carbon deposition rate was unclear. Nevertheless, an increasing amount of Ni dopant to Cu−Fe spinel retarded the conversion of dimethyl ether and led to high selectivity to CH4 and CO.