催化学报 ›› 2026, Vol. 86: 9-48.DOI: 10.1016/S1872-2067(26)65068-1
Shahla Karimib, Mehran Rezaeic,*(
), Jiguang Denga, Hongxing Daia, Ali Rastegarpanaha,*()
收稿日期:2025-12-01
接受日期:2026-01-21
出版日期:2026-07-05
发布日期:2026-06-12
通讯作者:
*电子信箱: ali.rastegarpanah@bjut.edu.cn (A. Rastegarpanah),基金资助:
Shahla Karimib, Mehran Rezaeic,*(), Jiguang Denga, Hongxing Daia, Ali Rastegarpanaha,*()
Received:2025-12-01
Accepted:2026-01-21
Online:2026-07-05
Published:2026-06-12
About author:Mehran Rezaei received his Ph.D. in Chemical Engineering in 2006 from Iran University of Science and Technology. He is currently a full Professor at the Faculty of Chemical, Petroleum and Gas Engineering at Iran University of Science and Technology. He has an extensive academic and industrial research record, having published more than 300 papers in international peer-reviewed journals. His work has had significant practical impact, with over 40 types of catalysts successfully developed and commercialized at the industrial scale. He has received numerous prestigious awards, including recognition as a National Distinguished Researcher and as an Outstanding Researcher by the Iranian Academy of Sciences. He currently serves as an Assistant Editor of the International Journal of Hydrogen Energy and as a Subject Editor of Process Safety and Environmental Protection.Supported by:摘要：
化石燃料消耗造成的温室气体大量排放, 特别是在能源领域, 迫切需要发展氢能等清洁能源替代技术. 甲烷分解(MD)可制备无二氧化碳清洁氢气并副产高价值碳纳米材料, 是低碳制氢的重要路线, 常用的催化剂包括金属氧化物和贵金属. 贵金属因其独特的电子结构和良好的催化性能而受到广泛关注. 因此, 本综述系统梳理贵金属催化剂(包括Pt、Pd、Rh、Ru、Ir和Au)在甲烷分解中的研究进展, 重点阐述不同贵金属的催化性能、反应机理与活性位点特征. 同时总结贵金属作为活性组分与助剂的双重作用, 当与过渡金属结合时, 贵金属可以调节电子相互作用、增加分散、抑制失活等, 为它们在甲烷分解催化中的双重功能提供了新的视角. 此外, 还综述分析反应条件的影响, 包括WHSV、进料比和CH4分压, 以将反应条件与催化性能联系起来. 归纳提高催化性能的策略, 例如评估各种活性位点、探索合成策略、考察载体和助剂的作用, 以及利用等离子体辅助还原. 最后, 面向高效、稳定、低成本甲烷分解催化剂的开发需求, 提出该领域未来发展方向与研究路线图.
Shahla Karimi, Mehran Rezaei, Jiguang Deng, Hongxing Dai, Ali Rastegarpanah. 甲烷分解用贵金属基催化剂的最新进展: 性能、机理与优化[J]. 催化学报, 2026, 86: 9-48.
Shahla Karimi, Mehran Rezaei, Jiguang Deng, Hongxing Dai, Ali Rastegarpanah. Recent advances in noble metal-based catalysts for methane decomposition: Performance, mechanism, and optimization[J]. Chinese Journal of Catalysis, 2026, 86: 9-48.
| Advantage | Challenge | Lab-scale conversion a |
|---|---|---|
| Steam methane reforming (SMR) CH4 + H2O ↔ CO + 3H2; ΔH298K = 206 kJ/mol | ||
| (1) Inexpensive H2 production technology (2) High efficiency (3) High H/C ratio (4) Suitable for high-pressure processes | (1) release of greenhouse gases into the atmosphere (2) need for downstream separation and purification steps (3) involvement of a complex network of reactions, including the water gas shift reaction | 35%-80% |
| Dry methane reforming (DMR) CH4 + CO2 ↔ 2CO + 2H2; ΔH298K = 247 kJ/mol | ||
| (1) Uses CO2 for hydrogen production (2) Applicable in the Fischer-Tropsch synthesis process | (1) greenhouse gas emissions (2) expensive equipment (3) complex downstream processes required for H2 purification (4) more energy-intensive process than SMR (5) easy carbon deposition | Up to 50% conversion |
| Partial methane oxidation (PMO) CH4 + 0.5O2 ⇆ CO + 2H2; ΔH298K = −36 kJ/mol | ||
| (1) Extremely short contact time (2) High selectivity and efficiency | (1) dependence on pure O2 feed (2) byproducts of soot formation (3) high COx emissions and possible NOx emissions (4) a hot spot may occur in the catalyst bed | 40%-95% conversion H2 selectivity >75% |
| Methane decomposition (MD) CH4 → C + 2H2; ΔH298K = 75.4 kJ/mol | ||
| (1) Low greenhouse gas emissions (2) Simple and single-step process (3) High-quality H2 production (4) Easy to separate solid carbon as a byproduct (5) Solid carbon is generated as value-added nanocarbons | (1) at an early stage of development (2) instability of catalysts; effective regeneration strategies are required (3) minor unconverted methane in the outlet stream | 30%-96% conversion H2 yield 26%-90% |
Table 1 Summary of H2 production technologies. The table presents a comparative overview of different methods in terms of their advantages, disadvantages, and potential for scale-up.
| Advantage | Challenge | Lab-scale conversion a |
|---|---|---|
| Steam methane reforming (SMR) CH4 + H2O ↔ CO + 3H2; ΔH298K = 206 kJ/mol | ||
| (1) Inexpensive H2 production technology (2) High efficiency (3) High H/C ratio (4) Suitable for high-pressure processes | (1) release of greenhouse gases into the atmosphere (2) need for downstream separation and purification steps (3) involvement of a complex network of reactions, including the water gas shift reaction | 35%-80% |
| Dry methane reforming (DMR) CH4 + CO2 ↔ 2CO + 2H2; ΔH298K = 247 kJ/mol | ||
| (1) Uses CO2 for hydrogen production (2) Applicable in the Fischer-Tropsch synthesis process | (1) greenhouse gas emissions (2) expensive equipment (3) complex downstream processes required for H2 purification (4) more energy-intensive process than SMR (5) easy carbon deposition | Up to 50% conversion |
| Partial methane oxidation (PMO) CH4 + 0.5O2 ⇆ CO + 2H2; ΔH298K = −36 kJ/mol | ||
| (1) Extremely short contact time (2) High selectivity and efficiency | (1) dependence on pure O2 feed (2) byproducts of soot formation (3) high COx emissions and possible NOx emissions (4) a hot spot may occur in the catalyst bed | 40%-95% conversion H2 selectivity >75% |
| Methane decomposition (MD) CH4 → C + 2H2; ΔH298K = 75.4 kJ/mol | ||
| (1) Low greenhouse gas emissions (2) Simple and single-step process (3) High-quality H2 production (4) Easy to separate solid carbon as a byproduct (5) Solid carbon is generated as value-added nanocarbons | (1) at an early stage of development (2) instability of catalysts; effective regeneration strategies are required (3) minor unconverted methane in the outlet stream | 30%-96% conversion H2 yield 26%-90% |
Fig. 1. Publication trend of noble-metal-based catalysts: The figure illustrates processes of H2 production from methane via MD, DRM, and SMR, showing their roles as active catalysts and promoters. Data were collected from Google Scholar using predefined keywords, with no year limit on the publications, including all available articles up to October 2025.
Fig. 2. Catalytic performance and methane decomposition behavior: (a) the effect of temperature and CeO2 doping on Pt/CeO2 catalyst at GHSV of 3400 h-1 [58], and (b) time evolution of CH4 dissociation and H2 formation at 1727 °C on the surfaces of the Pt80 and Ni20Pt60 clusters over 200 ps [59]. Reprinted with permission from [59]. Copyright under exclusive license to The Materials Research Society 2025.
| Catalyst | Reaction condition | Surface area (m2/g) | Conversion (H2 yield) (%) | TOF a (s-1) | Ref. | |
|---|---|---|---|---|---|---|
| Pt-based catalysts | ||||||
| 1 wt% Pt/γ-Al2O3 | T = 750 °C, pure CH4 steam = 2 mL/min | 147 | 64 (63) | 0.37 | [ | |
| 1 wt% Pt/γ-Al2O3-1 wt% Nd2O3 | 150 | 57 (56) | 0.33 | |||
| 1 wt% Pt/γ-Al2O3-10 wt% Nd2O3 | 146 | 80 (79) | 0.46 | |||
| 5 wt% Pt/CeO2 | T = 600 °C, GHSV = 3400 h-1 | — | 36.7 (30.7) | — | [ | |
| 5 wt% Pt/CeO2-10 wt% La2O3 | 32.6 (31.8) | — | ||||
| 5 wt% Pt/CeO2-23.7 wt% Pr6O11 | 38.5 (32.4) | — | ||||
| 5 wt% Pt/CeO2-14.5 wt%ZrO2 | 38.2 (28.7) | — | ||||
| Pt-unsupported | T = 900 °C, WHSV = 12000 mL/(gcat·h) (reported as F/W) | — | 40 | — | [ | |
| 2 wt% Pt/SiO2 | T = 500 °C, time = 120 min, CH4 circulating 0.20 mmol (initial partial pressure 2.7 kPa) and Ar (6.7 kPa) | — | 20 | — | [ | |
| 0.8 wt% Pt/SiO2 Particle size = 12 nm | T = 450 °C, flow rate = 1 NL/min, volume of catalyst = 20 cm3 | 230 | 9 | — | [ | |
| Particle size = 23 nm | < 50 | 36 | — | |||
| Particle size = 47 nm | — | ca. 30 | — | |||
| 1 wt% Pt/MCM-41 | T = 700 °C, time = 288.5 min, P = 1 atm, WHSV = 42000 CH4 mL/(g·h) | — | 22 | 2.2 | [ | |
| AC | T = 850 °C, time = ca. 65 min, CH4 flow rate = 10 mL/min | 1154 | ca. 0.19 mmol/(min·g) | — | [ | |
| 1 wt% Pt/AC | — | 0.28 | 0.09 | |||
| 5 wt% Pt/AC | — | 0.28 | 0.02 | |||
| 10 wt% Pt/AC | — | ca. 0.20 | 0.007 | |||
| 20 wt% Pt/AC | 919 | 0.12 | 0.002 | |||
| Pt-promoted catalysts | ||||||
| 15 wt% Ni-0.1 wt%-Pt/MgAl2O4 | T = 550 °C, time = 35 min, flow rate = 80 mL/min, N2:CH4 = 7:1 | — | 10 | 0.003 | [ | |
| Ni-31 wt% Pt | T = 700 °C, time = 60 min, WHSV=12000 mL/(gcat·h) (reported as F/W) | — | 55 | — | [ | |
| 30 mol% Ni-70 mol% Pt | T = 800 °C, time = 60 min, WHSV = 15000 mL/(g·h) | — | 11 | — | [ | |
| 50 mol% Ni-50 mol% Pt | 10 | — | ||||
| 90 mol% Ni-1 mol% Pt | ca. 60 | — | ||||
| Pt | 18 | — | ||||
| 30 wt% Fe-1 wt% Pt/MCM-41 | T = 750 °C, P = 1 atm, WHSV = 42000 CH4 mL/(g·h) | — | 64 (38) | 0.0620 | [ | |
| 20 wt% Ni-1 wt% Pt/MCM-41 | T = 700 °C, time = ca. 225 min, P = 101.3 kPa, WHSV = 0.0432 CH4 mL/(g·h) | — | (40) | 6.29×10-8 | [ | |
| 5wt% Ni-Pt/SiO2 Pt/Ni molar ratio = 0.1 | T = 550 °C, time =1 h, P = 101 kPa, CH4 flow rate = 40 mL/min | — | 12 | 0.1048 | [ | |
| 20 wt% Ni-xPt/CeO2 | 0.05 | T = 700 °C, time = 30 min, CH4 flow rate = 150 mL/min | — | (45) | 0.00737 | [ |
| 0.1 | 69.4 | (48) | 0.00786 | |||
| 0.2 | 73.8 | (53) | 0.0087 | |||
| 55 wt% Ni-15 wt% Cu-2 wt% Pt/MgO•Al2O3 | T = 600 °C, time = 600 min, WHSV = 48000 mL/(g·h), CH4:N2 = 3:17 | 123.6 | 60 | 0.0029 | [ | |
Table 2 Studies on Pt catalysts in the MD process: The data are categorized according to Pt-based and Pt-promoted, along with reaction conditions, and catalytic performance.
| Catalyst | Reaction condition | Surface area (m2/g) | Conversion (H2 yield) (%) | TOF a (s-1) | Ref. | |
|---|---|---|---|---|---|---|
| Pt-based catalysts | ||||||
| 1 wt% Pt/γ-Al2O3 | T = 750 °C, pure CH4 steam = 2 mL/min | 147 | 64 (63) | 0.37 | [ | |
| 1 wt% Pt/γ-Al2O3-1 wt% Nd2O3 | 150 | 57 (56) | 0.33 | |||
| 1 wt% Pt/γ-Al2O3-10 wt% Nd2O3 | 146 | 80 (79) | 0.46 | |||
| 5 wt% Pt/CeO2 | T = 600 °C, GHSV = 3400 h-1 | — | 36.7 (30.7) | — | [ | |
| 5 wt% Pt/CeO2-10 wt% La2O3 | 32.6 (31.8) | — | ||||
| 5 wt% Pt/CeO2-23.7 wt% Pr6O11 | 38.5 (32.4) | — | ||||
| 5 wt% Pt/CeO2-14.5 wt%ZrO2 | 38.2 (28.7) | — | ||||
| Pt-unsupported | T = 900 °C, WHSV = 12000 mL/(gcat·h) (reported as F/W) | — | 40 | — | [ | |
| 2 wt% Pt/SiO2 | T = 500 °C, time = 120 min, CH4 circulating 0.20 mmol (initial partial pressure 2.7 kPa) and Ar (6.7 kPa) | — | 20 | — | [ | |
| 0.8 wt% Pt/SiO2 Particle size = 12 nm | T = 450 °C, flow rate = 1 NL/min, volume of catalyst = 20 cm3 | 230 | 9 | — | [ | |
| Particle size = 23 nm | < 50 | 36 | — | |||
| Particle size = 47 nm | — | ca. 30 | — | |||
| 1 wt% Pt/MCM-41 | T = 700 °C, time = 288.5 min, P = 1 atm, WHSV = 42000 CH4 mL/(g·h) | — | 22 | 2.2 | [ | |
| AC | T = 850 °C, time = ca. 65 min, CH4 flow rate = 10 mL/min | 1154 | ca. 0.19 mmol/(min·g) | — | [ | |
| 1 wt% Pt/AC | — | 0.28 | 0.09 | |||
| 5 wt% Pt/AC | — | 0.28 | 0.02 | |||
| 10 wt% Pt/AC | — | ca. 0.20 | 0.007 | |||
| 20 wt% Pt/AC | 919 | 0.12 | 0.002 | |||
| Pt-promoted catalysts | ||||||
| 15 wt% Ni-0.1 wt%-Pt/MgAl2O4 | T = 550 °C, time = 35 min, flow rate = 80 mL/min, N2:CH4 = 7:1 | — | 10 | 0.003 | [ | |
| Ni-31 wt% Pt | T = 700 °C, time = 60 min, WHSV=12000 mL/(gcat·h) (reported as F/W) | — | 55 | — | [ | |
| 30 mol% Ni-70 mol% Pt | T = 800 °C, time = 60 min, WHSV = 15000 mL/(g·h) | — | 11 | — | [ | |
| 50 mol% Ni-50 mol% Pt | 10 | — | ||||
| 90 mol% Ni-1 mol% Pt | ca. 60 | — | ||||
| Pt | 18 | — | ||||
| 30 wt% Fe-1 wt% Pt/MCM-41 | T = 750 °C, P = 1 atm, WHSV = 42000 CH4 mL/(g·h) | — | 64 (38) | 0.0620 | [ | |
| 20 wt% Ni-1 wt% Pt/MCM-41 | T = 700 °C, time = ca. 225 min, P = 101.3 kPa, WHSV = 0.0432 CH4 mL/(g·h) | — | (40) | 6.29×10-8 | [ | |
| 5wt% Ni-Pt/SiO2 Pt/Ni molar ratio = 0.1 | T = 550 °C, time =1 h, P = 101 kPa, CH4 flow rate = 40 mL/min | — | 12 | 0.1048 | [ | |
| 20 wt% Ni-xPt/CeO2 | 0.05 | T = 700 °C, time = 30 min, CH4 flow rate = 150 mL/min | — | (45) | 0.00737 | [ |
| 0.1 | 69.4 | (48) | 0.00786 | |||
| 0.2 | 73.8 | (53) | 0.0087 | |||
| 55 wt% Ni-15 wt% Cu-2 wt% Pt/MgO•Al2O3 | T = 600 °C, time = 600 min, WHSV = 48000 mL/(g·h), CH4:N2 = 3:17 | 123.6 | 60 | 0.0029 | [ | |
| Catalyst | Reaction condition | Surface area (m2/g) | Conversion (H2 yield) (%) | TOF (s-1) a | Ref. | |
|---|---|---|---|---|---|---|
| Pd-based catalysts | ||||||
| 25 mol% Pd/Al2O3 | T = 700 °C, time = 50 min, flow rate = 80 mL/min | — | ca. 6 | — | [ | |
| Pd-Ni/Al2O3 | T = 700 °C, time = 500 min, flow rate = 80 mL/min | — | 34 | — | [ | |
| Pd-Co/Al2O3 | 21 | — | ||||
| Pd-Fe/Al2O3 | 12 | — | ||||
| Pd-Rh/Al2O3 | 12 | — | ||||
| 5 wt% Pd/Al2O3 | T = 700 °C, time = 30 min, CH4 flow rate = 20 mL/min, PCH4 = 101 kPa | — | ca. 9.5 | 0.030 | [ | |
| Au/Al2O3 | 0 | 0 | ||||
| Pd1-Au1/Al2O3 Pd/Au molar ratio = 1/1 | ca. 8.5 | 0.027 | ||||
| Pd3-Au1/Al2O3 Pd/Au molar ratio = 3/1 | ca. 7.5 | 0.024 | ||||
| Pd-Co/Al2O3 | 8.0 | 0.025 | ||||
| Pd-Fe/Al2O3 | 9.0 | 0.029 | ||||
| Pd-Cu/Al2O3 | 2.5 | 0.008 | ||||
| Pd-Ni/Al2O3 | 12.5 | 0.040 | ||||
| 10 wt% Pd/AC | T = 850 °C, time = 4 h, CH4 flow rate = 54 mL/min, WHSV = 1620 mL/(g·h) | 1085.05 | 52.5 | 0.011 | [ | |
| 10 wt% Pd/CB | 100.05 | 28.5 | 0.0061 | |||
| 5 wt% Pd/AC | T = 850 °C, time = 4 h, CH4 flow rate = 54 mL/min, WHSV =1620 mL/(g·h) | 896.73 | 27 | 0.0115 | [ | |
| 10 wt% Pd/AC | 751.56 | 53 | 0.0113 | |||
| 0.5 wt% Pd/ZSM-5 Si/Al = 25 | T = 800 °C, time = 150 min, flow rate = 16 mL/min | — | ca. 4.5 | 0.017 | [ | |
| Si/Al = 140 | 2.5 | 0.010 | ||||
| Si/Al = 750 | 15 | 0.060 | ||||
| AC | T = 850 °C, time = ca. 240 min, CH4 flow rate = 10 mL/min | 1154 | 0 mmol/min·g | — | [ | |
| 1 wt% Pd/AC | — | 0 | 0 | |||
| 5 wt% Pd/AC | — | 4.1 | 0.145 | |||
| 10 wt% Pd/AC | — | 7.5 | 0.133 | |||
| 20 wt% Pd/AC | 864 | 8 | 0.071 | |||
| 5 wt% Pd/TiO2 | T = 250 °C, flow rate of N2 + CH4 (12.5 vol%) = 40 mL/min | — | 0.25 | 0.000198 | [ | |
| 5 wt% Pd/Al2O3 | 0.13 | 0.000103 | ||||
| 5 wt% Pd/SiO2 | 0.05 | 0.000039 | ||||
| 5 wt% Pd/MgO | 0.02 | 0.000016 | ||||
| Pd-promoted catalysts | ||||||
| Ni-Pd/CNT | T = 600 °C, time = 300 min 30 mol% CH4/N2 | — | 45 | 0.0088 | [ | |
| 1 wt% Ni-1 wt% Pd/Al2O3 | T = 800 °C, time = 240 min, CH4:Ar flow rate = 10:5 mL/min | 212.8 | 24.6 | 0.0215 | [ | |
| 2 wt% Pd/Al2O3 | 195.3 | 15.7 | 0.0124 | |||
| 1 wt% Ni-1 wt% Pd/Al2O3 | T = 800 °C, time = 240 min, CH4:Ar flow rate = 10:5 mL/min | 196.7 | 16.5 | 0.0144 | [ | |
| 2 wt% Pd/Al2O3 | 182.9 | 13.0 | 0.0103 | |||
| 20 wt% Ni-xPd/Al2O3 | 5 | T = 750 °C, time = 600 min, WHSV = 12000 mL/(g·h), CH4:N2 = 3:7 | 72.7 | 11 | 0.0071 | [ |
| 10 | 45.8 | 54 | 0.0707 | |||
| 15 | 26.9 | 72 | 0.0094 | |||
| 20 | 12.3 | 68 | 0.0089 | |||
| T = 650 °C, time = 230 min, CH4 flow rate = 20 mL/min | 64.8 | 35 | 0.0102 | [ | ||
| 20 wt% Ni-1 wt% Pd/MCM-41 | T = 700 °C, time = ca. 235 min, P = 101.3 kPa, WHSV = 0.0432 CH4 mL/(g·h) | — | (60) | 9.43×10-8 | [ | |
| 4.5 wt% Fe-0.5 wt% Pd/Al2O3 | T = 700 °C, CH4 flow rate = 10 mL/min | — | (82) | 0.0056 | [ | |
| 55 wt% Ni-15 wt% Cu-xPd/MgO•Al2O3 | 2 | T = 600 °C, time = 600 min, WHSV = 48000 mL/(g·h),, CH4:N2 = 3:17 | 124.0 | 58 | 0.0055 | [ |
| 4 | 105.3 | 60 | 0.0057 | |||
| 6 | 94.2 | 56 | 0.0053 | |||
| 50 wt% Ni-15 wt% Cu-0.9 wt% Pd/Al2O3 | T = 750 °C, time = 6 h, WHSV = 18000 mL/(g·h) | 2.4 | ca. 80 | 0.0209 | [ | |
| 50 wt% Ni-15 wt% Cu-0.3 wt% Pd/Al2O3 | T = 750 °C, time = 6 h, WHSV = 18000 mL/(g·h) | 2.8 | 77 | 0.0202 | [ | |
| Ni-Pd/SiO2 Pd/(Pd + Ni) mole ratio = 0.05 | T = 650 °C, time = 6 h, P = 101 kPa, CH4 flow rate = 60 mL/min | — | 16 | — | [ | |
| 27.5wt%Ni-2.5wt%Pd/Carbon nanofiber Pd/(Pd + Ni) mole ratio = 0.5 | T = 550 °C, time = 50 h, PCH4 = 101 kPa, CH4 flow rate = 50 mL/min | — | 7 | 0.0277 | [ | |
| 5 wt% Ni-0.9 wt% Pd/SiO2 | T = 550 °C, time = 4 h, P = 101 kPa, CH4 flow rate = 40 mL/min | — | 11 | 0.0961 | [ | |
| 20 wt% Ni-0.4 wt% Pd/MgAl2O4 | T = 700 °C, time = 30 min, CH4 flow rate = 150 mL/min | 29.3 | (57) | 0.0187 | [ | |
| 50 wt% Ni-xPd/SBA-15 | 0.2 | T = 700 °C, time = 30 min, CH4 flow rate = 150 mL/min | 198.2 | (52) | 0.0068 | [ |
| 0.4 | 201.8 | (59) | 0.0077 | |||
Table 3 Studies on Pd catalysts in the MD process: The data are categorized according to Pd-based and Pd-promoted, along with reaction conditions, and catalytic performance.
| Catalyst | Reaction condition | Surface area (m2/g) | Conversion (H2 yield) (%) | TOF (s-1) a | Ref. | |
|---|---|---|---|---|---|---|
| Pd-based catalysts | ||||||
| 25 mol% Pd/Al2O3 | T = 700 °C, time = 50 min, flow rate = 80 mL/min | — | ca. 6 | — | [ | |
| Pd-Ni/Al2O3 | T = 700 °C, time = 500 min, flow rate = 80 mL/min | — | 34 | — | [ | |
| Pd-Co/Al2O3 | 21 | — | ||||
| Pd-Fe/Al2O3 | 12 | — | ||||
| Pd-Rh/Al2O3 | 12 | — | ||||
| 5 wt% Pd/Al2O3 | T = 700 °C, time = 30 min, CH4 flow rate = 20 mL/min, PCH4 = 101 kPa | — | ca. 9.5 | 0.030 | [ | |
| Au/Al2O3 | 0 | 0 | ||||
| Pd1-Au1/Al2O3 Pd/Au molar ratio = 1/1 | ca. 8.5 | 0.027 | ||||
| Pd3-Au1/Al2O3 Pd/Au molar ratio = 3/1 | ca. 7.5 | 0.024 | ||||
| Pd-Co/Al2O3 | 8.0 | 0.025 | ||||
| Pd-Fe/Al2O3 | 9.0 | 0.029 | ||||
| Pd-Cu/Al2O3 | 2.5 | 0.008 | ||||
| Pd-Ni/Al2O3 | 12.5 | 0.040 | ||||
| 10 wt% Pd/AC | T = 850 °C, time = 4 h, CH4 flow rate = 54 mL/min, WHSV = 1620 mL/(g·h) | 1085.05 | 52.5 | 0.011 | [ | |
| 10 wt% Pd/CB | 100.05 | 28.5 | 0.0061 | |||
| 5 wt% Pd/AC | T = 850 °C, time = 4 h, CH4 flow rate = 54 mL/min, WHSV =1620 mL/(g·h) | 896.73 | 27 | 0.0115 | [ | |
| 10 wt% Pd/AC | 751.56 | 53 | 0.0113 | |||
| 0.5 wt% Pd/ZSM-5 Si/Al = 25 | T = 800 °C, time = 150 min, flow rate = 16 mL/min | — | ca. 4.5 | 0.017 | [ | |
| Si/Al = 140 | 2.5 | 0.010 | ||||
| Si/Al = 750 | 15 | 0.060 | ||||
| AC | T = 850 °C, time = ca. 240 min, CH4 flow rate = 10 mL/min | 1154 | 0 mmol/min·g | — | [ | |
| 1 wt% Pd/AC | — | 0 | 0 | |||
| 5 wt% Pd/AC | — | 4.1 | 0.145 | |||
| 10 wt% Pd/AC | — | 7.5 | 0.133 | |||
| 20 wt% Pd/AC | 864 | 8 | 0.071 | |||
| 5 wt% Pd/TiO2 | T = 250 °C, flow rate of N2 + CH4 (12.5 vol%) = 40 mL/min | — | 0.25 | 0.000198 | [ | |
| 5 wt% Pd/Al2O3 | 0.13 | 0.000103 | ||||
| 5 wt% Pd/SiO2 | 0.05 | 0.000039 | ||||
| 5 wt% Pd/MgO | 0.02 | 0.000016 | ||||
| Pd-promoted catalysts | ||||||
| Ni-Pd/CNT | T = 600 °C, time = 300 min 30 mol% CH4/N2 | — | 45 | 0.0088 | [ | |
| 1 wt% Ni-1 wt% Pd/Al2O3 | T = 800 °C, time = 240 min, CH4:Ar flow rate = 10:5 mL/min | 212.8 | 24.6 | 0.0215 | [ | |
| 2 wt% Pd/Al2O3 | 195.3 | 15.7 | 0.0124 | |||
| 1 wt% Ni-1 wt% Pd/Al2O3 | T = 800 °C, time = 240 min, CH4:Ar flow rate = 10:5 mL/min | 196.7 | 16.5 | 0.0144 | [ | |
| 2 wt% Pd/Al2O3 | 182.9 | 13.0 | 0.0103 | |||
| 20 wt% Ni-xPd/Al2O3 | 5 | T = 750 °C, time = 600 min, WHSV = 12000 mL/(g·h), CH4:N2 = 3:7 | 72.7 | 11 | 0.0071 | [ |
| 10 | 45.8 | 54 | 0.0707 | |||
| 15 | 26.9 | 72 | 0.0094 | |||
| 20 | 12.3 | 68 | 0.0089 | |||
| T = 650 °C, time = 230 min, CH4 flow rate = 20 mL/min | 64.8 | 35 | 0.0102 | [ | ||
| 20 wt% Ni-1 wt% Pd/MCM-41 | T = 700 °C, time = ca. 235 min, P = 101.3 kPa, WHSV = 0.0432 CH4 mL/(g·h) | — | (60) | 9.43×10-8 | [ | |
| 4.5 wt% Fe-0.5 wt% Pd/Al2O3 | T = 700 °C, CH4 flow rate = 10 mL/min | — | (82) | 0.0056 | [ | |
| 55 wt% Ni-15 wt% Cu-xPd/MgO•Al2O3 | 2 | T = 600 °C, time = 600 min, WHSV = 48000 mL/(g·h),, CH4:N2 = 3:17 | 124.0 | 58 | 0.0055 | [ |
| 4 | 105.3 | 60 | 0.0057 | |||
| 6 | 94.2 | 56 | 0.0053 | |||
| 50 wt% Ni-15 wt% Cu-0.9 wt% Pd/Al2O3 | T = 750 °C, time = 6 h, WHSV = 18000 mL/(g·h) | 2.4 | ca. 80 | 0.0209 | [ | |
| 50 wt% Ni-15 wt% Cu-0.3 wt% Pd/Al2O3 | T = 750 °C, time = 6 h, WHSV = 18000 mL/(g·h) | 2.8 | 77 | 0.0202 | [ | |
| Ni-Pd/SiO2 Pd/(Pd + Ni) mole ratio = 0.05 | T = 650 °C, time = 6 h, P = 101 kPa, CH4 flow rate = 60 mL/min | — | 16 | — | [ | |
| 27.5wt%Ni-2.5wt%Pd/Carbon nanofiber Pd/(Pd + Ni) mole ratio = 0.5 | T = 550 °C, time = 50 h, PCH4 = 101 kPa, CH4 flow rate = 50 mL/min | — | 7 | 0.0277 | [ | |
| 5 wt% Ni-0.9 wt% Pd/SiO2 | T = 550 °C, time = 4 h, P = 101 kPa, CH4 flow rate = 40 mL/min | — | 11 | 0.0961 | [ | |
| 20 wt% Ni-0.4 wt% Pd/MgAl2O4 | T = 700 °C, time = 30 min, CH4 flow rate = 150 mL/min | 29.3 | (57) | 0.0187 | [ | |
| 50 wt% Ni-xPd/SBA-15 | 0.2 | T = 700 °C, time = 30 min, CH4 flow rate = 150 mL/min | 198.2 | (52) | 0.0068 | [ |
| 0.4 | 201.8 | (59) | 0.0077 | |||
| Catalyst | Reaction condition | Surface area (m2/g) | Conversion (H2 yield) (%) | TOF (s-1) a | Ref. |
|---|---|---|---|---|---|
| Rh-based catalysts | |||||
| 1 wt% Rh/γ-Al2O3 | T = 400 °C, pure CH4 steam = 2 mL/min | 266 | 45 | 0.138 | [ |
| 1 wt% Rh/γ-Al2O3-1 wt% Nd2O3 | 237 | 50 | 0.153 | ||
| 1 wt% Rh/γ-Al2O3-10 wt% Nd2O3 | 227 | 39 | 0.012 | ||
| 2 wt% Rh/ZSM-5 (Si/Al = 55) | T = 500 °C, time = 30 min, Ar + 12.5 vol% CH4 | — | 1 | 0.0006 | [ |
| 0.5 wt% Rh/CeO2 | T = 600 °C, GHSV = 3400 h-1 | — | 34 (ca. 32) | — | [ |
| 5 wt% Rh/SiO2 | T = 500 °C, time = 120 min, CH4 circulating 0.20 mmol (initial partial pressure 2.7 kPa) and Ar (6.7 kPa) | — | 38 | — | [ |
| Rh-promoted catalysts | |||||
| 10 wt% Co-1 wt% Rh/TiO2 | T = 600 °C, time = 300 min, P = 1 atm, CH4:N2 = 1:1, WHSV = 15000 mL/(g·h) | 156 | 22 | 0.048 | [ |
| 20 wt% Ni-1 wt% Rh/MCM-41 | T = 700 °C, time = ca. 233.3 min, P = 101.3 kPa, WHSV = 0.0432 CH4 mL/(g·h) | — | (30) | 4.72 × 10-8 | [ |
| LaNi0.95Rh0.05O3 | T = 450 °C, time = ca. 325 min, CH4 = 3 vol%, flow rate = 200 mL/min, WHSV = 2 × 105 mL/(g·h) | 8 | 25 | — | [ |
| Ni-Rh/SiO2 Rh/Ni molar ratio = 0.1 | T = 550 °C, time = 1 h, PCH4 = 101 kPa, CH4 flow rate = 40 mL/min | — | ca. 14 | 0.122 | [ |
Table 4 Studies on the Rh-based and promoted catalysts in the MD process under the reaction conditions.
| Catalyst | Reaction condition | Surface area (m2/g) | Conversion (H2 yield) (%) | TOF (s-1) a | Ref. |
|---|---|---|---|---|---|
| Rh-based catalysts | |||||
| 1 wt% Rh/γ-Al2O3 | T = 400 °C, pure CH4 steam = 2 mL/min | 266 | 45 | 0.138 | [ |
| 1 wt% Rh/γ-Al2O3-1 wt% Nd2O3 | 237 | 50 | 0.153 | ||
| 1 wt% Rh/γ-Al2O3-10 wt% Nd2O3 | 227 | 39 | 0.012 | ||
| 2 wt% Rh/ZSM-5 (Si/Al = 55) | T = 500 °C, time = 30 min, Ar + 12.5 vol% CH4 | — | 1 | 0.0006 | [ |
| 0.5 wt% Rh/CeO2 | T = 600 °C, GHSV = 3400 h-1 | — | 34 (ca. 32) | — | [ |
| 5 wt% Rh/SiO2 | T = 500 °C, time = 120 min, CH4 circulating 0.20 mmol (initial partial pressure 2.7 kPa) and Ar (6.7 kPa) | — | 38 | — | [ |
| Rh-promoted catalysts | |||||
| 10 wt% Co-1 wt% Rh/TiO2 | T = 600 °C, time = 300 min, P = 1 atm, CH4:N2 = 1:1, WHSV = 15000 mL/(g·h) | 156 | 22 | 0.048 | [ |
| 20 wt% Ni-1 wt% Rh/MCM-41 | T = 700 °C, time = ca. 233.3 min, P = 101.3 kPa, WHSV = 0.0432 CH4 mL/(g·h) | — | (30) | 4.72 × 10-8 | [ |
| LaNi0.95Rh0.05O3 | T = 450 °C, time = ca. 325 min, CH4 = 3 vol%, flow rate = 200 mL/min, WHSV = 2 × 105 mL/(g·h) | 8 | 25 | — | [ |
| Ni-Rh/SiO2 Rh/Ni molar ratio = 0.1 | T = 550 °C, time = 1 h, PCH4 = 101 kPa, CH4 flow rate = 40 mL/min | — | ca. 14 | 0.122 | [ |
Fig. 3. H2 production and TEM images of spent catalysts at 800 C and 0.1 WHSV: (a) H2 production graph along with surface area, (b) AB after 60 h, (c) AC after 8 h, (d) Ru-AC after 60 h, (e) ZSM-5 after 8 h, and (f) Ru-ZSM-5 after 8 h [119]. Reprinted with permission from [119]. Licensed under CC BY-NC 3.0.
Fig. 4. Comparative chart of Ru, Ir noble metals: Comparison of the performance of Ru, Ir-based [58,66,117,119], and Ru, Ir-promoted [68,116] catalysts in methane decomposition. Note: WHSV refers to mass-based flow rates (mL/(g·h)), while GHSV denotes volumetric hourly space velocity. When insufficient information was not reported, values are presented as originally stated in the literature.
Fig. 5. Evolution of CH4 decomposition on the Pt: (a) representation of H atom dissociation from CH4 on the Pt80 surface, (b) representation of H2 molecule formation on the Pt80 surface (the colors of the atoms are determined based on their atomic charge) [59]. (a,b) Reprinted with permission from [59]. Copyright under exclusive license to The Materials Research Society 2025. (c) Methane decomposition as a function of temperature on a Pt cluster for the reaction simulated based on own DFT calculations, surface species with temperature, and (d) H2 desorption with temperature [147]. (c,d) Reprinted with permission from [147]. Copyright 2025 Elsevier B.V.
Fig. 6. Calculated transition state structures. H atoms are colored pink, C atoms - gray, (edge) Pd atoms - (dark) cyan. For Pd(211) and Pd(111) single-crystal surfaces, two periodically repeated supercells are shown [148]. Reprinted with permission from [148]. Copyright 2016 Elsevier Inc.
Fig. 7. Proposed pathway of methane decomposition by Ogihara et al. [71]: (a) on the Pd surface and (b) Pd-Au surface. Reproduced based on the data in Ref. [71]. Copyright 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd.
Fig. 8. Representation of the behavior of CH4 decomposition on Rh metallic particles: (a) Rh/γ-Al2O3 and (b) Rh/γ-Al2O3-Nd2O3 with 10 wt% Nd [100]. Reproduced based on the data in Ref. [100], Copyright 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd.
Fig. 9. DFT-based insights into methane decomposition over Ru clusters: (a) Evolution of methane decomposition on Ru13 cluster as a function of temperature: (a) Minimum energy pathway of CH4 dehydrogenation on the metal cluster of Ru, calculated by CI-NEB (Light gray: Ru atom, dark gray: C atom, white: H atom), (b) surface species distribution, (c) H2 desorption profile with temperature [147]. Reprinted with permission from [147]. Copyright 2025 Elsevier B.V.
Fig. 10. DFT-calculated atomic configurations and reaction mechanism of Au species on amorphous carbon: (a) DFT-relaxed atomic configuration of a pure Au cluster consisting of six Au atoms on amorphous carbon (Au/C). The top and the bottom panels are the side and the top views of the configuration, respectively. (b,c) DFT-relaxed atomic configurations of the IS (b) and the FS (c) of CH3-Au/C. CH3-Au/C, CH2-Au/C, CH-Au/C, and C-Au/C denote the configurations of the Au cluster, respectively, with the presence of CH3*, CH2*, CH*, and C*, representing intermediates and the carbon product of the CH4 pyrolysis. IS, TS, and FS are the initial, the transition, and the final states, respectively. The dashed lines pointed by the white arrows in a-c denote the interatomic distances, and (d) the mechanism contains five FSs corresponding to five elementary reactions [127]. Reprinted with permission from [127], Copyright 2020 NATURE COMMUNICATIONS.
Scheme 1. Qualitative schematic summarizing DFT-derived trends reported in the literature. This schematic illustrates how Ea and carbon adsorption strength are commonly linked to resistance to carbon deposition and then stability [32,44,136].
Fig. 11. The effect of reaction conditions in the MD process: CH4 conversion in various (a) WHSV [64,116] and (b) feed ratios [60,64] on catalysts containing noble metals. Note: The comparative plots are created based on conversion curves recorded in the literature; statistical deviations were typically not provided.
Fig. 12. TEM and HAADF-STEM characterization of Pd and Pd-Rh nanocubes under different thermal treatments: (a) Pd nanocubes at room temperature, (b) 3 min at 500 °C, (c-e) atomic structure and compositional analysis of Pd-Rh core-frame nano-cubes at room temperature, (f-h) 500 °C after annealing for 60 min, (e), (h) atomic resolution HAADF-STEM images of the regions marked in (d) and (g), respectively, (c), (f) EDS mapping together with corresponding HAADF-STEM images of individual Pd-Rh nanocubes (red = Pd, green = Rh) [161]. Reprinted with permission from [161], Copyright The Royal Society of Chemistry 2013.
| Noble metal | Support | Reaction condition | Surface area (m2/g) | Particle size (nm) | Dispersion (%) | CH4 conversion (%) | Ref. |
|---|---|---|---|---|---|---|---|
| 1 wt% Pt | γ-Al2O3 | T = 750 °C, pure CH4 steam = 2 mL/min | 147 | 1.6 | 71 | 64 | [ |
| γ-Al2O3-1 wt% Nd2O3 | 150 | 2.1 | 54 | 57 | |||
| γ-Al2O3-10 wt% Nd2O3 | 146 | 2.4 | 48 | 80 | |||
| 1 wt% Rh | γ-Al2O3 | T = 400 °C, pure CH4 steam = 2 mL/min | 266 | 1.0 | 100 | 45 | [ |
| γ-Al2O3-1 wt% Nd2O3 | 237 | 2.1 | 52 | 50 | |||
| γ-Al2O3-10 wt% Nd2O3 | 227 | 3.3 | 33 | 39 | |||
| 5 wt% Pt | CeO2 | T = 600 °C, GHSV = 3400 h-1 | — | — | — | 36.7 | [ |
| CeO2-10 wt% La2O3 | 32.6 | ||||||
| CeO2-23.7 wt% Pr6O11 | 38.5 | ||||||
| CeO2-14.5 wt% ZrO2 | 38.2 | ||||||
| 5 wt% Pd | TiO2 | T = 250 °C, flow rate of N2 + CH4 (12.5 vol%) = 40 mL/min | — | — | 13.0 | 0.25 | [ |
| Al2O3 | 12.8 | 0.13 | |||||
| SiO2 | 10.7 | 0.05 | |||||
| MgO | 9.5 | 0.02 | |||||
| 0.5 wt% Pd | ZSM-5 Si/Al = 25 | T = 800 °C, time = 150 min, flow rate =16 mL/min | — | — | — | ca. 4.5 | [ |
| Si/Al = 140 | 2.5 | ||||||
| Si/Al = 750 | 15 | ||||||
| 0.5 wt% Ir | CeO2 | T = 600 °C, GHSV = 3400 h-1 | — | — | — | 36.7 | [ |
| CeO2-10 wt% La2O3 | 36.2 | ||||||
| CeO2-23.7 wt% Pr6O11 | 33.6 | ||||||
| 20 wt% Pd | AC | T = 850 °C, time = ca. 240 min, flow rate of CH4 = 10 mL/min | 864 | 21.0 | — | 8 mmol/(min·g) | [ |
| 20 wt% Pt | AC | T = 850 °C, time = ca. 65 min, flow rate of CH4 = 10 mL/min | 919 | 7.2 | — | 12 mmol/(min·g) | [ |
| 10 wt% Pd | AC | T = 850 °C, time = 4 h, WHSV = 1620 mL/(h·g) | 751.56 | 9.6 | — | 53 | [ |
| 10 wt% Pd | AC | T = 850 °C, time = 4 h, CH4 flow rate = 54 cm3/min, WHSV = 1620 mL/(g·h) | 1085.05 | 760a | — | 52.5 | [ |
| CB | 100.05 | 200 | 28.5 |
Table 5 Reported studies on noble metal catalysts loaded on various supports for the MD reaction.
| Noble metal | Support | Reaction condition | Surface area (m2/g) | Particle size (nm) | Dispersion (%) | CH4 conversion (%) | Ref. |
|---|---|---|---|---|---|---|---|
| 1 wt% Pt | γ-Al2O3 | T = 750 °C, pure CH4 steam = 2 mL/min | 147 | 1.6 | 71 | 64 | [ |
| γ-Al2O3-1 wt% Nd2O3 | 150 | 2.1 | 54 | 57 | |||
| γ-Al2O3-10 wt% Nd2O3 | 146 | 2.4 | 48 | 80 | |||
| 1 wt% Rh | γ-Al2O3 | T = 400 °C, pure CH4 steam = 2 mL/min | 266 | 1.0 | 100 | 45 | [ |
| γ-Al2O3-1 wt% Nd2O3 | 237 | 2.1 | 52 | 50 | |||
| γ-Al2O3-10 wt% Nd2O3 | 227 | 3.3 | 33 | 39 | |||
| 5 wt% Pt | CeO2 | T = 600 °C, GHSV = 3400 h-1 | — | — | — | 36.7 | [ |
| CeO2-10 wt% La2O3 | 32.6 | ||||||
| CeO2-23.7 wt% Pr6O11 | 38.5 | ||||||
| CeO2-14.5 wt% ZrO2 | 38.2 | ||||||
| 5 wt% Pd | TiO2 | T = 250 °C, flow rate of N2 + CH4 (12.5 vol%) = 40 mL/min | — | — | 13.0 | 0.25 | [ |
| Al2O3 | 12.8 | 0.13 | |||||
| SiO2 | 10.7 | 0.05 | |||||
| MgO | 9.5 | 0.02 | |||||
| 0.5 wt% Pd | ZSM-5 Si/Al = 25 | T = 800 °C, time = 150 min, flow rate =16 mL/min | — | — | — | ca. 4.5 | [ |
| Si/Al = 140 | 2.5 | ||||||
| Si/Al = 750 | 15 | ||||||
| 0.5 wt% Ir | CeO2 | T = 600 °C, GHSV = 3400 h-1 | — | — | — | 36.7 | [ |
| CeO2-10 wt% La2O3 | 36.2 | ||||||
| CeO2-23.7 wt% Pr6O11 | 33.6 | ||||||
| 20 wt% Pd | AC | T = 850 °C, time = ca. 240 min, flow rate of CH4 = 10 mL/min | 864 | 21.0 | — | 8 mmol/(min·g) | [ |
| 20 wt% Pt | AC | T = 850 °C, time = ca. 65 min, flow rate of CH4 = 10 mL/min | 919 | 7.2 | — | 12 mmol/(min·g) | [ |
| 10 wt% Pd | AC | T = 850 °C, time = 4 h, WHSV = 1620 mL/(h·g) | 751.56 | 9.6 | — | 53 | [ |
| 10 wt% Pd | AC | T = 850 °C, time = 4 h, CH4 flow rate = 54 cm3/min, WHSV = 1620 mL/(g·h) | 1085.05 | 760a | — | 52.5 | [ |
| CB | 100.05 | 200 | 28.5 |
Fig. 13. Schematic model illustrating sintering resistance and redispersion: Sintering resistance against PMC or Ostwald ripening (OR) is provided by the combined effects of interparticle repulsion forces, arising from the effective double layer, and atom trapping at oxygen ion vacancies. Oi’’ denotes interstitial (labile) O2- in Kröger-Vink notation, whose concentration is determined by the equilibrium OO· ↔ VO·· + Oi’’ between lattice oxygen and oxygen ion vacancies [177]. Reprinted with permission from [177]. Licensee MDPI.
Fig. 14. The effect of various promoters on Pd-based catalysts: Dispersion, particle size, and surface area of Pd-M catalysts according to ref [184-186].
Fig. 15. The effect of promoters on Pt-based catalysts: TEM images of reduced Pt-M (M = Pd, Rh, and Ir) samples [188]. Reprinted with permission from [188]. Copyright 2019 Hydrogen Energy Publications LLC.
Fig. 16. Evaluation of synthesis methods: (a) schematic illustration of the 0.2Pt/m-Al2O3-H2 synthesis process, calcined at 400 °C and reduced in 5 vol% H2/N2 at 400 °C, (b,c) TEM, (d) TEM-EDS elemental mapping of 0.2Pt/m-Al2O3-H2 [202], (e) SEM/TEM of CeO2120 and Au/CeO2120, (f) CeO2140 and Au/CeO2140, (g) CeO2160 and Au/CeO2160, (h) CeO2180 and Au/CeO2180 [203], (j) catalysts prepared by impregnation and (k) one-pot, (l) apparent crystallite sizes of Pt0 for the catalysts submitted to additional thermal treatment as a function of synthesis temperature [206], and (m) stainless steel hollow wall structure preparation using the ELP method [213]. (a-d) Reprinted with permission from [202]. Copyright 2017 NATURE COMMUNICATIONS. (c-h) Reprinted with permission from [203]. Copyright 2022, Licensed under CC BY. (i,j) Reproduced based on the data in Ref. [206]. Copyright 2020 Elsevier Ltd. (m) Reprinted with permission from [213]. Copyright The Royal Society of Chemistry 2025.
Fig. 17. A schematic and images of catalysts reduced via plasma and H2: (a) a glow-discharge plasma, (b) schematic of AuPd/SBA-15, left: plasma reduction and right: H2 reduction [223], (c) SEM images of argon plasma reduced Au, (d) argon plasma reduced Pd, (e) hydrogen reduced Au at 500 °C, and (f) Hydrogen reduced Pd at 500 °C [224]. (b) Reproduced based on the data in Ref. [223], Copyright 2012 Elsevier Inc. (c-f) Reprinted with permission from [224]. Copyright 2015 The Chemical Industry and Engineering Society of China, and Chemical Industry Press.
Fig. 18. SEM images of the Pd-M/Al2O3 catalysts after MD reaction: (a) 5 wt% Pd/Al2O3, (b) Pd3-Au1/Al2O3, (c) Pd1-Au1/Al2O3, at 700 °C with a CH4 flow rate of 20 mL/min [71], (d) 25 mol% Pd/Al2O3, (e) Pd-Ag, (f) Pd-Cu, (g) Pd-Ni, (h) Pd-Co at 700 °C, (h1) at the initial stage of reaction, and (h2) after deactivation (H2/M = 200) at 800 °C [70]. (a-c) Reprinted with permission from [71], Copyright 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd., (d-h2) Reprinted with permission from [70], Copyright 2006 Elsevier Inc.
| Catalyst | Light-off/effective temperature a (°C) | Dominant carbon morphology | Deactivation mechanisms | Relative cost b | Regeneration robustness | Ref. | ||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|
| Pt-unsupported | 600-900 | CNT | encapsulation of Pt(o) inside CNTs | high | medium | [ | ||||||
| Ni-unsupported | 500-800 | CNO | encapsulation of Ni(o) by CNO | low | low | |||||||
| Ni-31 wt% Pt | 400-600 | CNTs with Ni(o)Pt(0) particles anchored on tip | activity retained; no dominant deactivation reported | medium | high | |||||||
| 20 wt% Pd/AC | 750-950 °C (stability tests) | ordered carbon filaments | activity retained, no dominant deactivation reported | high | high | [ | ||||||
| 20 wt% Pt/AC | less ordered carbonaceous deposit | covering of active sites by carbon | high | medium | ||||||||
| Pd-Cu/Al2O3 | Only single-temperature (700 °C) stability data were reported | CNF | segregation of Ag or Cu atoms at the surface of alloy particles | low-medium | medium | [ | ||||||
| Pd-Ag/Al2O3 | short-length CNF | high | medium | |||||||||
| Pd-Co/Al2O3 | 700-850 °C (stability tests) | CNF | gradual loss of active facets for carbon precipitation, leading to a decrease in the precipitation rate of carbon from the Pd-Co alloy, reduced catalytic activity with rise temperature | medium | medium | |||||||
| 10 wt% Ni-2 wt% Cu/SiO2 | 500-650 | MWNT | not explicitly discussed | medium | medium | |||||||
| 20 wt% Ni/MgAl2O4 | only single-temperature (700 °C) stability data were reported | MWCNTs | decreased BET surface area, strong interaction of aggregated NiO with the MgAl2O4 support | low | low | [ | ||||||
| 20 wt% Ni-0.4 wt% Pd/MgAl2O4 | MWCNTs | dctivity retained, no dominant deactivation reported | medium | medium-high | ||||||||
| 1wt% Rh/γ-Al2O3-1 wt% Nd2O3 | 400-700 | amorphous carbon | Rh sintering and carbon deposition | medium-high | medium | [ | ||||||
| 1wt% Rh/γ-Al2O3-10 wt% Nd2O3 | 400-700 | amorphous carbon | not explicitly discussed | high | ||||||||
| 3wt% Ru-AC | only single-temperature (800 °C) stability data were reported | CNT | weak metal-support interaction, separation of Ru from AC and covered by carbon | high | low-medium | [ | ||||||
| 3wt% Ru-ZSM-5 | CNT | activity decreases over time; no dominant deactivation mechanism explicitly reported. | high | medium | ||||||||
| 60 wt% Ni-5 wt% Mn-5 wt% Ru/Al2O3 | only single-temperature (750 °C) stability data were reported | CNF | smaller BET surface area and larger pore volume | medium | medium | [ | ||||||
| 60 wt% Ni-5 wt% Mn-10 wt% Ru/Al2O3 | CNF | activity decreases over time; no dominant deactivation mechanism explicitly reported | medium | medium-high | ||||||||
| 55 wt% Ni-15 wt% Cu-6wt%Pd/MgO•Al2O3 | 575-675 | filamentous carbon | decreased BET surface area and particle sintering | medium-high | medium | [ | ||||||
| 10 wt% Co-1 wt% Rh/TiO2 TCalcination = 500 oC | only single-temperature (600 °C) stability data were reported | short-ranged, fewer CNTs | support sintering along with the development of CNTs | medium-high | medium | |||||||
| TCalcination = 600 °C | CNTs with a more uniform diameter of 40-50 nm | not explicitly discussed | high | |||||||||
| TCalcination = 800 °C | a few CNTs with small diameters | the rutile phase’s compact shape and limited metal support interaction, the poor metal dispersion caused by the aggregation of Co-Rh particles on the support, and the low surface area of TiO2 | medium | [ | ||||||||
| 40 wt% Ni/amorphous silica (AS) | only single-temperature (700 °C) stability data were reported | graphene nanosheets (GNSs) | agglomeration of both NiO and metallic Ni0 particles, decrease in BET surface area and dispersion of Ni particles | low | low | [ | ||||||
| 40 wt% Ni/ZSM-5 Si/Al ratio -400 | MWCNTs | activity retained, no dominant deactivation reported | medium | high | ||||||||
| 10 wt% Ni/SiO2 | 500-500 | graphitic and some amorphous or encapsulating carbon | carbon encapsulation, sintering of Ni° crystallites | low-medium | low | [ | ||||||
| 10 wt% Ni-2 wt% Cu/SiO2 | 500-650 | MWNT | not explicitly discussed | medium | medium | |||||||
| 15 wt% MnO2-50 wt% NiO/FeAl2O4 | 500-600 | filamentous carbon | accumulation of particles, drop-in BET surface, rise of the quasi-liquid state in species | medium | low | [ | ||||||
Table 6 Comparative Overview of Noble Metals and Ni in Methane Decomposition.
| Catalyst | Light-off/effective temperature a (°C) | Dominant carbon morphology | Deactivation mechanisms | Relative cost b | Regeneration robustness | Ref. | ||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|
| Pt-unsupported | 600-900 | CNT | encapsulation of Pt(o) inside CNTs | high | medium | [ | ||||||
| Ni-unsupported | 500-800 | CNO | encapsulation of Ni(o) by CNO | low | low | |||||||
| Ni-31 wt% Pt | 400-600 | CNTs with Ni(o)Pt(0) particles anchored on tip | activity retained; no dominant deactivation reported | medium | high | |||||||
| 20 wt% Pd/AC | 750-950 °C (stability tests) | ordered carbon filaments | activity retained, no dominant deactivation reported | high | high | [ | ||||||
| 20 wt% Pt/AC | less ordered carbonaceous deposit | covering of active sites by carbon | high | medium | ||||||||
| Pd-Cu/Al2O3 | Only single-temperature (700 °C) stability data were reported | CNF | segregation of Ag or Cu atoms at the surface of alloy particles | low-medium | medium | [ | ||||||
| Pd-Ag/Al2O3 | short-length CNF | high | medium | |||||||||
| Pd-Co/Al2O3 | 700-850 °C (stability tests) | CNF | gradual loss of active facets for carbon precipitation, leading to a decrease in the precipitation rate of carbon from the Pd-Co alloy, reduced catalytic activity with rise temperature | medium | medium | |||||||
| 10 wt% Ni-2 wt% Cu/SiO2 | 500-650 | MWNT | not explicitly discussed | medium | medium | |||||||
| 20 wt% Ni/MgAl2O4 | only single-temperature (700 °C) stability data were reported | MWCNTs | decreased BET surface area, strong interaction of aggregated NiO with the MgAl2O4 support | low | low | [ | ||||||
| 20 wt% Ni-0.4 wt% Pd/MgAl2O4 | MWCNTs | dctivity retained, no dominant deactivation reported | medium | medium-high | ||||||||
| 1wt% Rh/γ-Al2O3-1 wt% Nd2O3 | 400-700 | amorphous carbon | Rh sintering and carbon deposition | medium-high | medium | [ | ||||||
| 1wt% Rh/γ-Al2O3-10 wt% Nd2O3 | 400-700 | amorphous carbon | not explicitly discussed | high | ||||||||
| 3wt% Ru-AC | only single-temperature (800 °C) stability data were reported | CNT | weak metal-support interaction, separation of Ru from AC and covered by carbon | high | low-medium | [ | ||||||
| 3wt% Ru-ZSM-5 | CNT | activity decreases over time; no dominant deactivation mechanism explicitly reported. | high | medium | ||||||||
| 60 wt% Ni-5 wt% Mn-5 wt% Ru/Al2O3 | only single-temperature (750 °C) stability data were reported | CNF | smaller BET surface area and larger pore volume | medium | medium | [ | ||||||
| 60 wt% Ni-5 wt% Mn-10 wt% Ru/Al2O3 | CNF | activity decreases over time; no dominant deactivation mechanism explicitly reported | medium | medium-high | ||||||||
| 55 wt% Ni-15 wt% Cu-6wt%Pd/MgO•Al2O3 | 575-675 | filamentous carbon | decreased BET surface area and particle sintering | medium-high | medium | [ | ||||||
| 10 wt% Co-1 wt% Rh/TiO2 TCalcination = 500 oC | only single-temperature (600 °C) stability data were reported | short-ranged, fewer CNTs | support sintering along with the development of CNTs | medium-high | medium | |||||||
| TCalcination = 600 °C | CNTs with a more uniform diameter of 40-50 nm | not explicitly discussed | high | |||||||||
| TCalcination = 800 °C | a few CNTs with small diameters | the rutile phase’s compact shape and limited metal support interaction, the poor metal dispersion caused by the aggregation of Co-Rh particles on the support, and the low surface area of TiO2 | medium | [ | ||||||||
| 40 wt% Ni/amorphous silica (AS) | only single-temperature (700 °C) stability data were reported | graphene nanosheets (GNSs) | agglomeration of both NiO and metallic Ni0 particles, decrease in BET surface area and dispersion of Ni particles | low | low | [ | ||||||
| 40 wt% Ni/ZSM-5 Si/Al ratio -400 | MWCNTs | activity retained, no dominant deactivation reported | medium | high | ||||||||
| 10 wt% Ni/SiO2 | 500-500 | graphitic and some amorphous or encapsulating carbon | carbon encapsulation, sintering of Ni° crystallites | low-medium | low | [ | ||||||
| 10 wt% Ni-2 wt% Cu/SiO2 | 500-650 | MWNT | not explicitly discussed | medium | medium | |||||||
| 15 wt% MnO2-50 wt% NiO/FeAl2O4 | 500-600 | filamentous carbon | accumulation of particles, drop-in BET surface, rise of the quasi-liquid state in species | medium | low | [ | ||||||
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