A Mini-Review on Lanthanum–Nickel-Based Perovskite-Derived Catalysts for Hydrogen Production via the Dry Reforming of Methane (DRM)
Abstract
:1. Introduction
2. Brief Summary of Ni-Based Catalysts for Methane Dry Reforming
3. Perovskites for DRM
3.1. La–Ni Perovskite-Derived Catalysts for DRM
3.2. A1A2BO3 Perovskite Catalysts
3.3. AB1B2O3 Perovskite Catalysts
3.4. A1A2B1B2O3 Perovskite Catalysts
3.5. Mesoporous/Supported Perovskite Catalysts
3.6. Three-Dimensionally Ordered (3DOM) Macroporous Perovskites
4. Kinetic and Mechanistic Considerations
- (1)
- Perovskite undergoes reduction (active metal should be reduced),
- (2)
- Perovskite is supported on basic oxide,
- (3)
- Rate of carbon dioxide dissociation is inconsiderable in comparison to that of methane,
- (4)
- Negligible surface coverage of hydrogen and carbon monoxide,
- (5)
- A part of active metal is carbon-free under DRM conditions.
5. Conclusions
- -
- LaNiO3 gained considerable attention due to the high affinity between CO2 and La2O3, which results in La2O2CO3 formation, as well as the strong metal–support interaction provided. The presence of La2O2CO3 plays a key role in the catalyst’s stability, as it can actively react with coke and act as an inhibitor against carbon accumulation on the nickel’s surface.
- -
- A-site partial substitutions with alkaline earth or rare earth metals into the perovskite matrix can both induce oxygen vacancies and modify the basicity of the surface of the catalyst, thereby improving coke resistance. The increased amount of lattice oxygen can also promote C–H activation, increase nickel dispersion, and increase the reducibility of the catalyst. Furthermore, redox chemistry of rare earth metals such as Sm, Pr, and Ce has a positive influence on the stability of the catalyst due to the fact that more oxygen for carbon removal is supplied.
- -
- B-site substitution can be reflected in two aspects. Non-reducible metals such as zirconium, and titanium can modify the structure and enhance the metal–support interaction, thus suppressing carbon deposition. On the other hand, reducible metals such as Fe, Co, Ru, and Cu can provide a synergetic effect which can be either beneficial or detrimental. To illustrate this point, the addition of iron generates a nickel-containing alloy which improves the stability of the perovskite. Moreover, the redox chemistry of the iron induces oxygen for coke removal due to the dynamic profile of the catalyst, which undergoes dealloying via oxidation by carbon dioxide and re-alloying via its reduction by carbon species. A smaller nickel particle size and decreased reducibility are related to the addition of iron or cobalt. In addition, cobalt can serve as a promoter owing to its high oxygen affinity, which aids in carbon gasification. Certain amounts of copper and manganese can also improve the catalytic behavior of the perovskite oxides in terms of both activity and stability.
- -
- The preparation of perovskites requires considerably high calcination temperatures to produce materials with considerably small surface areas, thus affecting their catalytic behavior. One method to overcome this problem is to disperse perovskite on certain supports, such as SBA-15 and MCM-41, leading to smaller perovskite particles. Another method is to synthesize porous perovskite catalysts by using templating methods.
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
References
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Perovskite | Operating Conditions | CH4 Conversion Order | Carbon Deposition | Ref. |
---|---|---|---|---|
La0.95Ba0.05NiO3 La0.90Ba0.10NiO3 La0.85Ba0.15NiO3 La0.80Ba0.20NiO3 La0.75Ba0.25NiO3 La0.70Ba0.30NiO3 | T = 650–750 °C WHSV = 60,000 mL g−1 h−1 CH4:CO2:He = 1:1:8 | La0.90Ba0.10NiO3 > La0.85Ba0.15NiO3~La0.85Ba0.15NiO3 > La0.75Ba0.25NiO3 > La0.70Ba0.30NiO3 Ba-substituted catalysts outperformed the Sr and Mg ones. | - | [97] |
LaNiO3 La0.95Ca0.05NiO3 La0.90Ca0.10NiO3 La0.70Ca0.30NiO3 La0.50Ca0.50NiO3 La0.20Ca0.80NiO3 | T = 650–750 °C WHSV = 720,000 mL g−1 h−1 CH4:CO2 = 1:1 | La0.50Ca0.50NiO3~La0.70Ca0.30NiO3 > La0.95Ca0.05NiO3 > La0.20Ca0.80NiO3 > La0.90Ca0.10NiO3 > LaNiO3 | - | [98] |
LaNiO3 La0.9Sr0.1NiO3 La0.8Sr0.2NiO3 La0.7Sr0.3NiO3 La0.6Sr0.4NiO3 Ni(5%)/La2O3 | T = 700 °C CH4:CO2 = 1:1 | LaNiO3 > La0.6Sr0.4NiO3 > Ni(5%)/La2O3 > La0.9Sr0.1NiO3 The order of activity depends on the content of strontium. | no coke no coke no coke no coke no coke no coke | [88] |
La2Ni0.3Al0.7O3 La0.8Sr0.2Ni0.3Al0.7O2.9 La0.5Sr0.5Ni0.3Al0.7O2.75 La0.2Sr0.8 Ni0.3Al0.7O2.6 | T = 750 °C WHSV = 15,000 mL g−1 h−1 CH4:CO2:N2 = 1:1:8 | La0.2Sr0.8 Ni0.3Al0.7O2.6 > La0.5Sr0.5Ni0.3Al0.7O2.75 > La0.8Sr0.2Ni0.3Al0.7O2.9 Ca-substituted catalysts were more stable but less active. | 8.71%—15 h 8.31%—15 h 3.21%—15 h - | [99] |
LaNiO3 La0.98Pr0.02NiO3 La0.90Pr0.10NiO3 La0.60Pr0.40NiO3 | T = 700 °C WHSV = 600,000 mL g−1 h−1 CH4:CO2 = 1:1 | La0.50Pr0.10NiO3 > LaNiO3 > La0.98Pr0.02NiO3 > La0.60Pr0.40NiO3 | 63%—8 h 51%—8 h traces—8 h 52%—8 h | [100] |
LaNiO3 La0.90Ce0.10NiO3 La0.70Ce0.30NiO3 La0.50Ce0.50NiO3 | T = 600–800 °C GHSV = 10,000 h−1 CH4:CO2 = 1:1 | LaNiO3 > La0.90Ce0.10NiO3 > La0.50Ce0.50NiO3 > La0.70Ce0.30NiO3 | - | [101] |
Perovskite | Operating Conditions | CH4 Conversion Order | Carbon Deposition | Ref. |
---|---|---|---|---|
LaNiO3 LaNi0.8Zn0.2O3 LaNi0.6Zn0.4O3 LaNi0.4Zn0.6O3 LaNi0.2Zn0.8O3 LaZnO3 | T = 750 °C WHSV = 180,000 mL g−1 h−1 CH4:CO2:He = 1:1:1 | LaNi0.8Zn0.2O3 > LaNi0.6Zn0.4O3 > LaNiO3 > LaNi0.4Zn0.6O3 > LaNi0.2Zn0.8O3 > LaZnO3 | 0.7%—75 h 0.4%—75 h - - - - | [109] |
LaNiO3 LaNi0.9Ru0.1O3 LaNi0.8Ru0.2O3 La3.5Ru4.0O3 | T = 750 °C WHSV = 7200 mL mL g−1 h−1 CH4:CO2 = 1:1 | LaNiO3 > LaNi0.9Ru0.1O3 > LaNi0.8Ru0.2O3~La3.5Ru4.0O3 | 65.7%—14 h 20.3%—14 h 6.7%—14 h 0.9%—14 h | [110] |
LaNiO3 La2NiO4 La2Ni0.5Fe0.5O4 LaNi0.5Fe0.5O3 | T = 750 °C WHSV = 120,000 mL g−1 h−1 CH4:CO2 = 1:1 | LaNiO3~La2NiO4 > La2Ni0.5Fe0.5O4 > LaNi0.5Fe0.5O3 | 31.0%—4 h 18.0%—4 h 3%—4 h 9%—4 h | [111] |
LaNiO3 LaNi0.8Cu0.2O3 LaNi0.6Cu0.4O3 LaNi0.4Cu0.6O3 LaNi0.2Cu0.8O3 LaCuO3 | T = 750 °C WHSV = 180,000 mL g−1 h−1 CH4:CO2:He = 1:1:1 | LaNiO3 > LaNi0.6Cu0.4O3 > LaNi0.4Cu0.6O3 > LaNi0.8Cu0.2O3 > LaNi0.2Cu0.8O3 > LaCuO3 | - - - - - - | [112] |
La2NiO4 La2Ni0.9Cu0.1O4 La2Ni0.8Cu0.2O4 La2Ni0.7Cu0.3O4 La2Ni0.6Cu0.4O4 | T = 750 °C WHSV = 18,000 mL g−1 h−1 CH4:CO2 = 1:1 | La2NiO4 > LaNi0.9Cu0.1O4 > LaNi0.8Cu0.2O4 > LaNi0.7Cu0.3O4 > LaNi0.6Cu0.4O4 | 0.4 gcg−1h−1—4 h 0.18 gcg−1h−1—5 h 0.01 gcg−1h−1—5 h 0.01 gcg−1h−1—5 h 0.01 gcg−1h−1—5 h | [113] |
LaNiO3 LaNi0.8Mn0.2O3 LaNi0.6Mn0.4O3 LaNi0.4Mn0.6O3 LaNi0.2Mn0.8O3 LaMnO3 | T = 750 °C GHSV = 15,000 mL g−1 h−1 CH4:CO2:N2 = 1:1:2 | LaNi0.6Mn0.4O3 > LaNi0.4Mn0.6O3 > LaNi0.8Mn0.2O3 > LaMnO3 > LaNi0.2Mn0.8O3 > LaNiO3 | - - - - - - | [114] |
Kinetic Parameters | Temperature Range (°C) | Ref. |
---|---|---|
Ni/La2O3 K1 k2 = 2.61 × 10−3exp(−4300/T) [mol g−1 s−1] K3 = 5.17 × 10−5exp(8700/T) [kPa−1] k4 = 5.35 × 10−1exp(−7500/T) [mol g−1 s−1] | 650–750 | [155] |
Ni/La2O3 derived from LaNiO3, at T = 700 °C K1 = 141 × 10−3 [kPa] k2 = 0.22326 × 10−3 [mol g−1 s−1] K3 = 15.98 × 10−3 [kPa] K4 = 13.22 × 10−3 [mol g−1 s−1] | 500–700 | [82] |
LaNiO3 K1 = 279.55exp(−7502.5/T) [kPa−1] k2 = 12.27exp(−10,219.2/T) [mol g−1 s−1] K3 k4 = 0.034exp(−6968.2/T) [kPa−1 mol g−1 s−1] | 650–750 | [157] |
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Georgiadis, A.G.; Charisiou, N.D.; Goula, M.A. A Mini-Review on Lanthanum–Nickel-Based Perovskite-Derived Catalysts for Hydrogen Production via the Dry Reforming of Methane (DRM). Catalysts 2023, 13, 1357. https://doi.org/10.3390/catal13101357
Georgiadis AG, Charisiou ND, Goula MA. A Mini-Review on Lanthanum–Nickel-Based Perovskite-Derived Catalysts for Hydrogen Production via the Dry Reforming of Methane (DRM). Catalysts. 2023; 13(10):1357. https://doi.org/10.3390/catal13101357
Chicago/Turabian StyleGeorgiadis, Amvrosios G., Nikolaos D. Charisiou, and Maria A. Goula. 2023. "A Mini-Review on Lanthanum–Nickel-Based Perovskite-Derived Catalysts for Hydrogen Production via the Dry Reforming of Methane (DRM)" Catalysts 13, no. 10: 1357. https://doi.org/10.3390/catal13101357