1. School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China 2. Tianjin Key Laboratory of Membrane Science and Desalination Technology, Tianjin University, Tianjin 300072, China 3. School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832003, China 4. Key Laboratory for Green Chemical Technology of Ministry of Education, Research and Development Center for Petrochemical Technology, Tianjin University, Tianjin 300072, China
Copper has received extensive attention in the field of catalysis due to its rich natural reserves, low cost, and superior catalytic performance. Herein, we reviewed two modification mechanisms of co-catalyst on the coordination environment change of Cu-based catalysts: (1) change the electronic orbitals and geometric structure of Cu without any catalytic functions; (2) act as an additional active site with a certain catalytic function, as well as their catalytic mechanism in major reactions, including the hydrogenation to alcohols, dehydrogenation of alcohols, water gas shift reaction, reduction of nitrogenous compounds, electrocatalysis and others. The influencing mechanisms of different types of auxiliary metals on the structure-activity relationship of Cu-based catalysts in these reactions were especially summarized and discussed. The mechanistic understanding can provide significant guidance for the design and controllable synthesis of novel Cu-based catalysts used in many industrial reactions.
Due to the Cu–Ni alloy interaction, Ni is important for glycerol reforming in inert atmosphere, generating in situ H2 that is used for acetol hydrogenation to propylene glycol
Aqueous glycerol solution (10 vol-%), H2 (4 MPa, 30 mL?min–1), WHSV= 2 h–1, catalyst (1.25 g), T = 523 K
Glycerol conv.:>90%, 1,2-PDO yield: 50%
(1) Ni site is not necessary when H2 is added. (2) The high acidity of ZSM-5 favors the formation of acrolein when compared to the catalysts supported on Al2O3
Cu–Ni promotes the hydrogenolysis of C–O bonds and limits the cleavage of C–C bonds, and helps glycerol selectively convert to 1,2-PDO via a dehydration-hydrogenation pathway
The introduction of Pd facilitates spillover of in situ formed H2 on carbon materials, which is resulted in the unique cluster-in-cluster alignment of the CuPd nanostructures
[73]
CuPd/TiO2-Na
5 wt-% Cu, Cu/Pd molar ratio= 1.67:1
Wet impregnation method
Aqueous glycerol solution (20 wt-%, 50 mL), H2 (0.7 MPa), Na (0.5 wt-%) catalyst (0.3 g), T = 493 K, stirring at 480 r?min–1
Glycerol solution in methanol (40 wt-%), H2 (2.5 MPa), catalyst (9%, based on glycerol), T = 473 K
Glycerol conv.: 94.1%, 1,2-PDO select.: 98.3%, the catalyst can be reused
The presence of Pd contributes to the transform of Cu2+ to Cu+/Cu
[72]
Pd0.04Cu0.4/Mg5.56Al2O8.56
7.23 wt-% Cu, Cu/Pd molar ratio= 10:1
Co-precipitation method
Aqueous glycerol solution (75 wt-%, 8 g), H2 (2 MPa), catalyst (1 g), T = 453 K, t = 10 h
Glycerol conv.: 76.9%, 1,2-PDO select.: 97.2%, the catalyst can be reused for 5 times
(1) The presence of Pd facilitates the H2 overflow from Pd to Cu. (2) The catalytic activity is better when using methanol and ethanol as solvents, because the adsorption of water on the catalyst surface is stronger than methanol and ethanol, which hinders the availability of glycerol
[71]
Pd0.04Cu0.4/Mg5.56Al2O8.56
7.23 wt-% Cu, Cu/Pd molar ratio= 10:1
Co-precipitation method
Glycerol solution in alcohol (75 wt-%, 8 g), H2 (2 MPa), catalyst (1 g), T = 453 K, t = 10 h
In methanol solvent: glycerol conv.: 89.5%, 1,2-PDO select.: 98.2%, in ethanol solvent: glycerol conv.: 88%, 1,2-PDO select.: 99.6%
[71]
Cu–Pt/SiO2
10 wt-% Cu, Cu/Pt molar ratio= 1:0.2
Wet impregnation method
Glycerol solution in methanol (40 wt-%, 20 g), H2 (4 MPa), catalyst (1.5 g), T = 473 K, stirring at 600 r?min–1
Glycerol conv.: 100%, 1,2-PDO select.: 96%
The strong reduction of Pt promotes the reduction of Cu2+
[74]
Ru–Cu/SiO2
5 wt-% Cu, Cu/Ru molar ratio= 1:3
Wet impregnation method
Glycerol (120 mL), H2 (8 MPa), catalyst (0.9 g), catalyst/glycerol mass ratio= 0.006, T = 513 K, t = 5 h, stirring at 1000 r?min–1
Glycerol conv.: 39.2%, 1,2-PDO select.: 85.9%
The incorporation of Ru increases the glycerol conversion, while reduces the 1,2-PDO selectivity as Ru contributes to the cleavage of C–C bond
(1) The improvement of these two catalysts is ascribed to the interaction between Ru and Re on the Cu sites instead of additional M sites. (2) Glycerol solution in alcohol is better than aqueous glycerol solution, because the adsorption of water on the catalyst surface is stronger than methanol, ethanol and other alcohols, which hinders the accessibility of glycerol. (3) The addition of external hydrogen helps increase the glycerol conversion and 1,2-PDO selectivity
[75]
Re0.02Cu0.4/Mg5.6Al1.98O8.57
7.23 wt-% Cu, Cu/Re molar ratio= 20:1
Co-precipitation method
Solution of glycerol (75 wt-%, 8.0 g), H2 (2.0 MPa), catalyst (1.0 g), T = 453 K, t = 10 h
Glycerol conv.: 63%, 1,2-PDO select.: 45%, no change in catalyst structure after 24 h
The presence of Re increases the acidity and promotes the cleavage of C–C bonds
[76]
CuAg/γ-Al2O3
Cu+Ag/γ-Al2O3 = 2.7 mmol, Cu/Ag molar ratio= 7:3
Incipient wetness impregnation method
Aqueous glycerol solution (50 wt-%), H2 (1.5 MPa, initial pressure), (Cu+Ag)/glycerol molar ratio= 3:100, T = 473 K, t = 10 h, stirring at 400 r?min–1
Glycerol conv.: 27%, 1,2-PDO select.: 100%
Ag contributes to the H2 spillover to CuO and helps reduce CuO to active Cu sites
[79]
Cu–Ag/Al2O3
1 wt-% Ag
Incipient wetness impregnation method
Aqueous glycerol solution (15 wt-%, 1.32 cm3·h–1), H2 (360 cm3?min–1), hydrogen/glycerol mass ratio= 700:1, catalyst (8.7 g), at ambient hydrogen pressure and a low gradient temperature from 443 K to 378 K
1,2-PDO yield: 98.3%
(1) Ag reduces the hydrogenation capacity, so double-layer catalysts are used. (2) The presence of Ag changes the surface chemical and electronic properties, reducing the cracking capacity of Cu
(1) The addition of Ag leads to sintering of the support or clogging of the supporting pores. (2) The Al2O3-supported catalyst is much more selective for 1,2-PDO
[91]
CuAg/TiO2
2 mmol Cu
Wet impregnation method
Glycerol conv.: 44%, 1,2-PDO select.: 62%
[91]
Tab.1
Fig.8
Catalysts
Composition of catalysts
Preparation methods
Reaction conditions
Catalytic performance
Comments
Ref.
Cu–Zn/SiO2
Cu/Zn molar ratio= 1:1
Coprecipitation method
H2 flow= 60 mL·min–1, WHSV= 2 h–1, catalyst (1.35 g), T = 523 K, P = 2 MPa
ethyl acetate conv.: 81.6%, EtOH select.: 93.8%
When Cu/Zn molar ratio= 1:1, Cu particles are the smallest, resulting in higher dispersion and catalytic activity
Cu0 is mainly responsible for the activation of H2. Cu+ is beneficial for adsorbing C=O group and activating GVL intermediate due to the presence of electron lone pair of oxygen. The electron-deficient CoOx formed can further activate the C=O of EL and GVL
[99]
Cu–Ni/Al2O3
10 wt-% Cu, 5 wt-% Ni
Incipient impregnation method
EL (1.0 mmol), solvent 2-butanol (3 mL), catalyst (100 mg), T = 423 K, t = 12 h, stirring at 600 r?min–1
EL conv.: 100%, GVL yield: 97%
Cu2+ species are prone to be reduced to Cu0/Cu+ and Ni2+ are inclined to be reduced to Ni0 at the same time, which provides more hydrogenating sites and results in higher activity
[98]
Tab.2
Fig.9
Fig.10
Fig.11
Catalysts
Composition of catalysts
Preparation methods
Reaction conditions
Catalytic performance
Comments
Ref.
CuNi/SiO2
20 wt-% Cu+Ni, Cu/Ni molar ratio= 1:1
Wet co-impregnation method
H2/CO= 1:1, GHSV= 2000 h–1, T = 548 K, P = 10 MPa
CO conv.: 12.1%, ROH select. based on carbon: (MeOH: 99%, C2+OH: 0.4%), MeOH STY: 167 g·kgcat–1·h–1
The CO adsorbed on Ni is basically an observation molecule that determines the surface structure, and methanol synthesis occurs on the Cu step
[61]
Cu–Ni/SiO2
20 wt-% Cu+Ni, Cu/Ni molar ratio= 2:1
Impregnation method
H2/CO volume ratio= 2:1, GHSV= 4000 h–1, T = 548 K, P = 10 MPa
CO conv.: 8.5%, ROH select. based on carbon: (MeOH: 99.7%, EtOH: 0.2%), MeOH STY: 0.19 kg·kgcat–1·h–1
(1) Coprecipitation and deposition-coprecipitation are more effective for preparing small and uniform Cu–Ni alloy NPs. (2) The uniform Cu–Ni alloy NPs are beneficial to the reaction. (3) Due to the formation of nickel carbonyl, the loss of Ni may emerge as a serious problem
[122]
Cu–Ni/SiO2
20 wt-% Cu+Ni, Cu/Ni molar ratio= 2:1
Co-precipitation method
H2/CO volume ratio= 2:1, GHSV= 4000 h–1, T = 548 K, P = 10 MPa
CO conv.: 14.3%, ROH select. based on carbon: (MeOH: 99.1%, EtOH: 0.2%), MeOH STY: 0.52 kg·kgcat–1·h–1
[122]
Cu–Ni/SiO2
20 wt-% Cu+Ni, Cu/Ni molar ratio= 2:1
Deposition-coprecipitation method
H2/CO volume ratio= 2:1, GHSV= 4000 h–1, T = 548 K, P = 10 MPa
CO conv.: 16.6%, ROH select. based on carbon: (MeOH: 99.2%, EtOH: 0.3%), MeOH STY: 0.66 kg·kgcat–1·h–1
[122]
CuFe
25 wt-% Cu, Cu/Fe molar ratio= 1:3
Wet-chemical method
H2/CO/N2 molar ratio= 65/32/3, GHSV= 6000 h–1, T = 493 K, P = 6 MPa, T = 24 h
The dual sites of Cu–FeCx facilitate the synthesis of higher alcohols. Cu acts as a site for the activation and insertion of CO, while FeCx is the site of CO dissociative activation and chain growth
[119]
Cu–Fe/N-CNT
Cu/Fe molar ratio= 15:1
Co-impregnation method
H2/CO= 2:1, GHSV= 6000 mL·g–1·h–1, quartz sand (1 mL), catalyst (200 mg), T = 493 K, P = 2 MPa
CO conv.: 20.9%, ROH select.: 27.2% (MeOH:31.2%, C2+OH: 68.8%)
The dispersion of Cu–Fe and the interaction between Cu, Fe and N-CNT are improved when doping N in CNT, and many surface basic sites are introduced
(1) A higher Cu/Fe ratio will favor the formation of alcohol, while a higher Fe/Cu ratio will favor the formation of hydrocarbon. (2) The surface content of Cu of the catalysts follows the order of Fe/Cu/SiO2>Cu/Fe/SiO2>Cu–Fe/SiO2. (3) The method of impregnating Fe first and then immersing Cu facilitates the higher ROH selectivity and STY, probably due to the lowest surface content of Cu and the formation of relatively smallest Fe3O4 particles on this catalyst
Cu is the active site for CO activation and insertion, and Fe2C is the active site for CO dissociation and carbon chain growth. The interaction between them promotes the formation of higher alcohols
The addition of Mn and cetyl trimethyl ammonium bromide facilitates the reduction of Cu2+ to Cu0 and the generation of Cu–Fe3C double active sites on ZnO supports
[116]
CuZnAl
Cu/Zn/Al molar ratio= 2:1:0.8
A complete liquid-phase method
Flow rate: 150 mL·min–1 (H2/CO= 2, v/v), T = 523 K, P = 4.5 MPa
CO conv.: 23%, ROH select.: 20% (MeOH: 55%, C2+OH: 45%)
Increasing the pH can reduce the size of Cu0 and increase the amount of reducible Cu+, and the probable amount of acid sites enhance the catalytic performance
[128]
Cu–Co/CNTs
Cu/Co molar ratio= 5:10
Co-impregnation method
H2/CO= 2:1, GHSV= 10000 mL·gcat–1·h–1, TOS= 7 h, T = 573 K, P = 4.5 MPa
CO conv.: 38.9%, CH4 select.: 48.5 C mol-%, C2–C4 select.: 14.0 C mol-%, CO2 select.: 1.7 C mol-%, ROH select.: 35.8 C mol-% (MeOH: 52.7 C mol-%, EtOH: 57.7 C mol-%, PrOH: 12.5 C mol-%, BuOH: 7.3 C mol-%), EtOH STY: 372.9 mg·gcat–1·h–1
Besides Cu0–Co0, the Co0–Co2+ also has two active sites for the synthesis of higher alcohols, because Co could stop carbon chain growth
More Co transfers into Co2C later in the reaction, which protects Cu@Co@Co2C from Co loss and the Cu sintering, resulting in higher ethanol selectivity
[109]
Cu/Co
Cu:Co molar ratio= 1:1.3
Use lysine as a surfactant template
H2/CO/N2 molar ratio= 65:32:3, GHSV= 10000 mL·h–1·g–1, catalyst (2 g), T = 573 K, P = 6 MPa
The mesopores of graphene-LaFeO3 promote the transfer of reactive molecules, and the formation of CuCo alloys results in high selectivity of higher alcohols
H2/CO/CO2 molar ratio= 4:2:1, catalysts (about 0.5 g), T = 713 K, t>12 h
MeOH yield: 2.5×10–6 mol·gcat–1·h–1
Au has no promotion on the catalyst
[123]
Ag–Cu/CrAl3O6
1% Ag to 5% Cu/CrAl3O6, Cr/Al molar ratio= 1:3
Wet aqueous impregnation method
MeOH yield: 2.5×10–7 mol·gcat–1·h–1
The formation of Ag2CrO4 and extra active sites enhance the activity
[123]
Tab.3
Catalysts
Composition of catalysts
Preparation methods
Reaction conditions
Catalytic performance
Comments
Ref.
NiCu/γ-Al2O3
9.6 wt-% Cu, 1.2 wt-% Ni, Cu/Ni molar ratio= 8:1
Atomic layer deposition method
H2/CO2 volume ratio= 3:1, total flow rate= 30?mL·min–1, catalyst (0.5 g), T = 523 K, P = 2.0?MPa
CO2 conv.: 6.4%, MeOH select.: 58.8%, MeOH yield: 1.5?mmol·g–1·h–1
This method provides higher alloy dispersion than impregnation method, promoting the synthesis of methanol
[157]
Cu–Ni/CeO2-nanotube
Cu/Ni molar ratio= 1:2
Impregnation method
CO2/H2/N2 molar ratio= 1:3:1, GHSV= 6000 h–1, catalyst (0.1 g), T = 533 K, P = 3.0 MPa
CO2 conv.: 17.8%, MeOH select.: 76%, MeOH STY: 18.1 mmol·gcat–1·h–1
The formation of CuNi alloy advances the reduction of CeO2, which produces numerous oxygen vacancies to adsorb and activate CO2
[154]
Cu/ZnO
0.4 mL ZnO
Deposition method
T = 540 K, = 0.45 MPa, = 0.05 MPa
MeOH yield: 0.16×1015 molecules·cm–2·s–1
Zn is converted to ZnO in ZnCu during the reaction, which makes ZnCu reach the activity of ZnO/Cu, suggesting the interaction between Cu and ZnO
[137]
Cu–Zn/reduced graphene oxide
10 wt-% Cu–Zn
Incipient wetness impregnation method
CO2/H2 = 1:3, GHSV= 2400 h–1, STY= 424 mgMeOH·gcat–1·h–1, T = 523 K, P = 1.5 MPa
CO2 conv.: 26%, MeOH select.: 5.1%, MeOH STY: 424 mg·gcat–1·h–1
Pyridine-N is a favorable site for hydrogen bond interaction and it can attract hydrogen donors to increase MeOH STY, resulting from the rGO reduced by hydrazine
[135]
CuO·ZnO·Al2O3
Cu:Zn molar ratio= 2:1
Co-precipitation method
CO2/H2 molar ratio= 1:3, GHSV= 40000 ·gCat–1·h–1, T = 523 K, P = 5 MPa
CO2 conv.: 12.9%, MeOH select.: 93.8%, MeOH yield: 1641.6 mL·gcat–1·h–1, the intrinsic activity: 531.3·m2Cu–1·h–1
(1) Intermetallic compounds bimetallic oxides and copper-f block element oxides show higher catalytic activity in producing methanol. (2) The close interaction facilitates electronic sharing between them and subsequent increase in catalytic activity
[155]
CuO·ZnO·Al2O3
Cu:Zn molar ratio= 2:1
Co-precipitation method
CO2/H2/CH4 molar ratio= 1:3:1, GHSV= 40000 ··h–1, T = 523 K, P = 5 MPa
CO2 conv.: 15.3%, MeOH select.: 95.3%, MeOH yield: 585.3 mL·gcat–1·h–1, the intrinsic activity: 189.4 ·m2Cu–1·h–1
[155]
Cu–Zn/γ-Al2O3
Cu/Zn molar ratio= 1:1
Incipient wetness impregnation method
H2/CO2 molar ratio= 3:1, GHSV= 500 h–1, catalyst (5 g), T = 543 K, P = 4 MPa
CO2 conv.: 0.192%, MeOH select.: 22.54%, MeOH STY= 16.36 g·kgCat–1·h–1
The high calcination temperature has a negative effect on the microstructure and Cu dispersion, which is not conducive to the methanol production
[134]
CuZn-BTC
Cu/Zn/BTC molar ratio= 1:1:0.56
“Acidic etching-self assembly” method
H2/CO2/N2 73:24:3, WHSV= 1500 mL·gcat–1·h–1, catalyst (0.5 g), T = 523 K, P = 4 MPa
The interaction between Pd, Cu and Zn contributes to the better performance and the formation of PdZn and PdCu alloys are selective for methanol and CO, respectively
[136]
Pd–Cu/SiO2
10 wt-% Cu, 5.7 wt-% Pd
Co-impregnation method
CO2/H2/Ar volume ratio= 24%:72%:4%, GHSV= 3600 mL (STP)·gcat–1·h–1, W/F = 6.2 gcat·h·mol–1, catalyst (0.2 g), T = 523 K, P = 4.1 MPa
The Pd–Cu alloy formation is the key factor for the promotion of catalytic activity
[148]
Tab.4
Fig.12
Catalysts
Composition of catalysts
Preparation methods
Reaction conditions
Catalytic performance
Comments
Ref.
Cu–NiO
10% Cu
Space-confinement method
H2O/EtOH (S/E) molar ratio= 6:1, GHSV= ∼180 h–1, WHSV= 2 gEtOH·gcat–1·h–1, T = 573 K
EtOH conv.: ∼100%, H2 yield: ∼5 mol/per mol of EtOH, : ∼13 mol/per mol of CH4 formed
The interaction of Cu–NiO surface enhances the catalytic activity and their close contact enlarges this effect
[168]
Cu–Ni/γ-Al2O3
6.6 wt-% Cu, 2 wt-% Ni
Incipient wetness impregnation method
DBO (2 mmol), styrene (4 mmol), mesitylene (2 mL), under N2, catalyst (0.40 g), T = 403 K, t = 24 h
DBO conv.: 52%, DBA select.:>99%
(1) The presence of styrene (H2 acceptor) contributes to the transformation of primary aliphatic alcohol to the corresponding aldehyde with high conversion. (2) The introduction of Ni decreases the size of Cu particles
[164]
Cu–Ni/γ-Al2O3
6.6 wt-% Cu, 2 wt-% Ni
Incipient wetness impregnation method
DBO (2 mmol), catalyst (0.40 g), styrene (8 mmol), mesitylene (2 mL), T = 423 K, t = 24 h
DBO conv.: 93%, DBA select.:>99%, after four cycles: DBO conv.: 73%, DBA select.:99%
[164]
Cu–Ni/γ-Al2O3
6.6 wt-% Cu, 2 wt-% Ni
Incipient wetness impregnation method
DBO (2 mmol), styrene (4 mmol), mesitylene (2 mL), N2 atmosphere, catalyst (0.4 g), T = 423 K, t = 24 h
DBO conv.: 93%, DBA select.:>99%
The addition of Ni greatly improves the hydrogenation of C=C bonds instead of C=O bonds, improving the styrene hydrogenation and obstructing the DBA rehydrogenation
[165]
Cu–Ni/Al2O3
10 wt-% Cu, 10 wt-% Ni
Impregnation method
Water/methanol mole ratio= 1.7:1, flow rate= 0.06 mL·min–1, T = 598 K
MeOH conv.: 96.1%, H2 yield: 2.08 mol·molMeOH–1, CO2 yield: 0.71 mol·molMeOH–1, CO yield: 0.13 mol·molMeOH–1, CH4 yield: 0.11 mol·molMeOH–1
The alloyed Cu inhibits the CO and CO2 hydrogenation during the methanol decomposition
[169]
Cu–Ni/ZrO2
1.5 wt-% Cu, 1.5 wt-% Ni
Deposition-precipitation method
total flow rate of O2 (5%)/He= 50 mL·min–1, GHSV= 30000 h–1, MeOH= 75 Torr, H2O= 12.75 Torr, O2 = 25.2 Torr, catalyst (0.1 g), T = 623 K
MeOH conv.: ∼100%, H2 select.: ∼60 mol-%, CO2 select.: ∼20 mol-%, CO, CH4 select.: ∼20 mol-%, the catalyst can be reused for 4 times
The reaction intermediates are mainly located in ZrO2 Cu and Ni are functioning in facilitating H2 overflow and released to raw materials
[160]
Ni–Cu/ZrO2
Ni/Cu molar ratio= 1:4
Precipitation method
MeOH/H2O molar ratio= 1:1, catalyst (0.3 g), T = 573 K, annealed at 623 K
MeOH conv.: 100%, H2 yield: 1.5 mol·molMeOH–1, CO yield: ∼0, CO2 yield: 0.5 mol·r–1
(1) Annealed at lower temperature can achieve the maximum hydrogen production. (2) Rich Cu results in lower Fermi level and enhances the adsorption of alcohol, further accelerating the convert into CO2
[161]
Ni–Cu/Y0.1Zr0.9O1.95
20 wt-% Ni+Cu, Ni/Cu molar ratio= 1:4
Coprecipitation method
MeOH/H2O molar ratio= 1:1, mixture rate= 1 cm3·h–1, GHSV=172 h–1, catalyst (0.3 g), T = 573 K
MeOH conv.: ∼28%, H2 select.: 99.8%
The catalyst doped Ce is the most active and the reduction of Ce4+ to Ce3+ becomes easier when solid solution of ZrO and CeO2 is formed
[163]
Ni–Cu/La0.1Zr0.9O1.95
MeOH conv.: ∼44%, H2 select.: 99.8%
Ni–Cu/Ce0.1Zr0.9O1.95
MeOH conv.: ∼60%, H2 select.: 100%
Cu–Zr
Cu/Zr molar ratio= 2:1
–
PMeOH = 0.0012 MPa, = 0.0024 MPa, Par = 0.0008 MPa, PHe = 0.0956 MPa, T = 550 K
MeOH conv.: ~100%, CO2 select.:>99.9%
The Cu-tetragonal ZrO2 interface is greatly beneficial to catalysis
Co is partly covered by carbon and Cu is located in the edge without carbon. The redistribution of active sites affects a lot on the catalytic activation
[170]
Au–Cu/MWCNT
20 wt-% Cu, 0.5 wt-% Au
Deposition-precipitation method
H2O/MeOH/O2 molar ratio= 1:1:0.4, mixture rate= 31.5 mL·min–1, GHSV= 26700 h–1, catalyst (0.1 g), T = 573 K
MeOH conv.: ~100%, H2 yield: ~3.1 ·molMeOH–1
(1) Defects on CNTs facilitate the electrons transfer, thereby promoting the reduction of CuO to Cu. (2) The presence of acid sites facilitates the stabilization of reactant intermediates
Benzyl alcohol (1.0 mmol), 1-phenylethanol (1.0 mmol), o-xylene (3 mL), at a relative pressure of 0.995, 0.1 MPa N2, catalyst (0.1 g), T = 423 K, T = 0.5 h
benzyl alcohol conv.: ~99%, β-phenylpropiophenone yield: ~99%, the catalyst can stable for five cycles without any loss of activity
(1) Alkaline support promotes dehydrogenation cross-coupling of primary and secondary benzyl alcohols, and acidic support promotes etherification of primary and secondary benzyl alcohols. (2) Ag activates Cu sites and obstructs their oxidation
[174]
Ru–Cu/ZnO–Al2O3
20 wt-% Cu, 1 wt-% Ru
Incipient wetness impregnation method
H2O/MeOH/O2 molar ratio= 1:1:0.4, total flow rate= 31.5 mL·min–1, GHSV= 26700 h–1, catalyst (0.2 g), T = 473 K, P = 0.1 MPa
MeOH conv.: 28%, H2 select.: 20%, CO select.: 0%, CO2 select.: 100%
(1) The adsorption and dissociation of H2 are easier to occur on precious metals, subsequently H2 spills over to accelerate the reduction of CuO to Cu2O. (2) Precious metal can enhance the adsorption of CH3OH during the dehydrogenation process. (3) Appropriate acidity favors the conversion of CH3OH. (4) The catalyst supported on ZrO2–Al2O3 shows lower CH3OH conversion than that of ZnO–Al2O3
[172]
Rh–Cu/ZnO–Al2O3
20 wt-% Cu, 1 wt-% Rh
Incipient wetness impregnation method
H2O/MeOH/O2 molar ratio= 1:1:0.4, total flow rate= 31.5 mL·min–1, GHSV= 26700 h–1, catalyst (0.2 g), T = 473 K, P = 0.1 MPa
MeOH conv.: 99%, H2 select.: 70.5%, CO select.: 0%, CO2 select.: 99.6%
[172]
Ag–Cu/ZnO–Al2O3
20 wt-% Cu, 1 wt-% Ag
Incipient wetness impregnation method
H2O/MeOH/O2 molar ratio= 1:1:0.4, total flow rate= 31.5 mL·min–1, GHSV= 26700 h–1, catalyst (0.2 g), T = 473 K, P = 0.1 MPa
MeOH conv.: 87%, H2 select.: 62.2%, CO select.: 0%, CO2 select.: 100%
[172]
Ir–Cu/ZnO–Al2O3
20 wt-% Cu, 1 wt-% Ir
Incipient wetness impregnation method
H2O/MeOH/O2 molar ratio= 1:1:0.4, total flow rate= 31.5 mL·min–1, GHSV= 26700 h–1, catalyst (0.2 g), T = 473 K, P = 0.1 MPa
MeOH conv.: 86%, H2 select.: 53%, CO select.: 0%, CO2 select.: 88%
[172]
Ru–Cu/ZrO2–Al2O3
20 wt-% Cu, 1 wt-% Ru
Incipient wetness impregnation method
H2O/MeOH/O2 molar ratio= 1:1:0.4, total flow rate= 31.5 mL·min–1, GHSV= 26700 h–1, catalyst (0.2 g), T = 473 K, P = 0.1 MPa
MeOH conv.: 31%, H2 select.: 24%, CO select.: 0%, CO2 select.: 100%
[172]
Rh–Cu/ZrO2–Al2O3
20 wt-% Cu, 1 wt-% Rh
Incipient wetness impregnation method
H2O/MeOH/O2 molar ratio= 1:1:0.4, total flow rate= 31.5 mL·min–1, GHSV= 26700 h–1, catalyst (0.2 g), T = 473 K, P = 0.1 MPa
MeOH conv.: 74%, H2 select.: 71%, CO select.: 15%, CO2 select. : 85%
[172]
Ag–Cu/ZrO2–Al2O3
20 wt-% Cu, 1 wt-% Ag
Incipient wetness impregnation method
H2O/MeOH/O2 molar ratio= 1:1:0.4, total flow rate= 31.5 mL·min–1, GHSV= 26700 h–1, catalyst (0.2 g), T = 473 K, P = 0.1 MPa
MeOH conv.: 48%, H2 select.: 64%, CO select.: 0%, CO2 select.: 97.3%
[172]
Ir–Cu/ZrO2–Al2O3
20 wt-% Cu, 1 wt-% Ir
Incipient wetness impregnation method
H2O/MeOH/O2 molar ratio= 1:1:0.4, total flow rate= 31.5 mL·min–1, GHSV= 26700 h–1, catalyst (0.2 g), T = 473 K, P = 0.1 MPa
MeOH conv.: 41%, H2 select.: 33%, CO select.: 0%, CO2 select.: 82.3%
[172]
Tab.5
Fig.13
Catalysts
Composition of catalysts
Preparation methods
Reaction conditions
Catalytic performance
Comments
Ref.
Cu–Ni/Ac
20 wt-% CuO+NiO, Cu/Ni molar ratio= 2:1
Wetness impregnation method
CO/H2O/N2 molar ratio= 4.5%:30.5%:65%, catalyst (0.25 g), T = 623 K
CO conv.: 95%
The size of the catalyst plays a more important role rather than Cu/Ni content
[185]
Cu–Ni/AC
62.7 wt-% Cu, Cu/Ni molar ratio= 1.56:1
Wetness impregnation method
CO/H2O molar ratio= 4.5%:30.6%, N2 balance, GHSV= 4000 h–1, catalyst (0.25 g), T = 623 K
CO conv.: 82.5%
Cu remains in Cu0 during the reaction and the CuNi alloy formation inhibits methane production
[188]
Ni–Cu/SiO2
10 wt-% Ni–Cu, Ni/Cu molar ratio= 5:5
In situ self-assembled core-shell precursor method
CO/H2O molar ratio= 5%:25%, He balance, the total flow rate= 50 mL·min–1, GHSV= 68000 h–1, catalyst (0.05 g), T = 673 K
CO conv.: 78.9%, H2 yield: 45%, TOF= 0.002 s–1
The highly dispersed NiCu alloy can promote the CO adsorption and activate hydroxyl on the SiO2 surface
In situ self-assembled core-shell precursor method
CO conv.: 96.8%, H2 yield: 53%, TOF= 0.004 s–1
OA can promote metal dispersion and enhance the interaction between metal and support
[187]
Cu–Ni/SiO2
–
Thermal decomposition precursor
H2O/CO= 4:1, GHSV= 3600 h–1, catalyst (1.0 g), T = 573 K, P = 0.1 MPa
CO conv.: 97.83%, CO2 select.: 98.64%
This preparation method contributes to the high dispersion of CuO and NiO
[194]
Cu–Ni/γ-Al2O3
10 wt-% Cu, 10 wt-% Ni
Co-precipitation method
H2 (60 vol-%), CO (1 vol-%), O2 (1 vol-%), He balance, GHSV= 60000 h–1, T = 473 K
Without H2O and CO2, CO conv.: 2.91 mmolCO·s–1·kgcat–1, with 10 vol-% H2O: 3.58 mmolCO·s–1·kgcat–1, with 10 vol-% CO2: 2.42 mmolCO·s-1·kgcat–1, with 10 vol-% H2O and 10 vol-% CO2: 2.51 mmolCO·s–1·kgcat–1
(1) The addition of H2O has a positive effect on CO conversion while the addition of CO2 has a negative effect. (2) CO conversion is in the order of Cu–Mn/Al2O3>Cu–Ni/Al2O3>Cu/Al2O3>Ni/Al2O3>Mn/Al2O3>Al2O3. (3) The formation of CuMn2O4 contributes to the high dispersion of Cu and Mn, resulting in high CO conversion
[193]
Cu–Mn/γ-Al2O3
10 wt-% Cu, 10 wt-% Mn
Co-precipitation method
H2 (60 vol-%), CO (1 vol-%), O2 (1 vol-%), He balance, GHSV= 60000 h–1, T = 473 K
Without H2O and CO2, CO conv.: 3.32 mmolCO·s–1·kgcat–1, with 10 vol-% H2O: 3.85 mmolCO·s–1·kgcat–1, with 10 vol-% CO2: 2.66 mmolCO·s–1·kgcat–1, with 10 vol-% H2O and 10 vol-% CO2: 3.11 mmolCO·s–1·kgcat–1
[193]
Ce0.7Cu0.1Fe0.2O2−δ
Ce/Cu/Fe molar ratio= 0.7:0.1:0.2
Sonochemical method
CO (2 vol-%), N2 balance, total gas flow rate= 100 mL·min–1, The flow rate of water vapor= 55 mL·min–1, GHSV= 48000 h–1, P = 0.1 MPa
CO conv.: 100%, H2 select.: 100%
Compared to Cu–Ni/CeO2, the activity of Cu–Fe/CeO2 is lower because Fe is more easily to be oxidized under reaction conditions
[191]
Ce0.75Cu0.1Ni0.15O2−δ
Ce/Cu/Ni molar ratio= 0.75:0.1:0.15
Cu0.3Fe0.7Ox
Cu/Fe molar ratio= 3:7
Aerosol-spray self-assembly method
2.2% CO/N2 stream (56 cm3·min–1), CO/H2O feed ratio= 1:7, GHSV= 42000 cm3·g–1·h–1, catalyst (20 mg), T = 523 K, P = 0.1 MPa, t = 140 h
Rate= 1.46×10–6 mol·m–2·s–1, TOF= 0.047 s–1, CO conv.: 50%
(1) The addition of Fe can promote the dispersion of Cu0 and enhance the adsorption of CO and CO2. (2) The addition of Al enhances the durability of the catalyst
[190]
Cu0.3Fe0.6Al0.1Ox
Cu/Fe/Al molar ratio= 3:6:1
Aerosol-spray self-assembly method
Rate= 3.98×10–6 mol·m–2·s–1, TOF= 0.136 s–1, CO conv.: 85%
[190]
CuPd/CeO2
30 wt-% Cu, 1 wt-% Pd
Incipient wetness impregnation method
CO (4 vol-%), CO2 (10 vol-%), air (2 vol-%), Ar (26 vol-%), H2 balance, H2O/CO molar ratio= 10:1
CO conv.: 77%
H2 prefers to be adsorbed and dissociated on Pd site, and H2 spillovers to CuO site, resulting in the congregation of reduced Cu accompanied with water desorption
[183]
Pd–Cu/CeO2
5 wt-% Cu, 1 wt-% Pd
Incipient wetness impregnation method
CO/H2O/CO2/H2/Air= 9.7%:22.8%:6.3%:37.9%:6.9% (1.4% O2), argon balance, a total flow rate of 132.5 mL·min–1, GHSV= 64400 h–1 (dry), catalyst (0.15 g), T = 533 K
H2 production rates: 122 μmol·g–1·s–1
Compared with Pt in Pt-Cu/CeO2, the Pd in Pd–Cu/CeO2 is more surrounded by Cu and the interaction between Cu and Pd is stronger
[184]
Pt–Cu/CeO2
5 wt-% Cu, 1 wt-% Pt
Incipient wetness impregnation method
H2 production rates: 160 μmol·g–1·s–1
[184]
Pt–Cu/ZnO/Al2O3
Cu/Zn molar ratio= 1:1, 0.05 wt-% Pt, 10 mol-% Al
Co-precipitation methods
CO/H2O/H2/CO2/N2 = 0.77:2.2:4.46:0.57:30, GHSV= 4800 mL·h–1·gcat–1, catalyst (0.05 g), T = 523 K
CO conv.: 78%, TOF=1.95×10–2 s–1
Pt promotes the H2 spillover from Pt to Cu to prohibit Cu from sintering and accelerates the reduction-oxidation cycle of Cu0 and Cu+
[182]
Au–Cu/CeO2
7 wt-% Cu, 1 wt-% Au
Incipient wetness impregnation method
A total flow rate of 200 mL·min–1, balanced to He, GHSV= 12000 h–1, WSV= 1.83 NL min–1·g–1, catalyst (0.1 g), T = 483 K, in WGS. CO/H2O/H2/CO2 = 4:9.4:37.9:3, in CO-PROX: CO/O2/H2 = 4:0.56:37.9, in OWGS: CO/H2O/H2/CO2/O2 = 4:9.4:37.9:3:0.56
In CO-PROX: CO conv.: 36%, in WGS: CO conv.: 1%, in OWGS: CO conv.: 35%, in CO-PROX: CO conv.: 37%, in WGS: CO conv.: 3.8%, in OWGS: CO conv.: 40%
The catalyst prepared by deposition-precipitation shows higher Au dispersion and oxygen storage capacity than the catalyst prepared by incipient wetness impregnation
[181]
Au–Cu/CeO2
7 wt-% Cu, 1 wt-% Au
Deposition-precipitation method
[181]
Au–CuO/CeO2
7 wt-% CuO, 1 wt-% Au
Incipient wetness impregnation method
A total flow rate of 200 mL·min–1, He to balance, GHSV= 12000 h–1, WSV= 1.83 NL min–1·g–1, catalyst (0.1 g), in CO-PROX: CO/H2/O2 = 0.5:30:0.5 (in % by vol.), T = 372 K, in WGS: CO/H2O/H2/CO2 = 0.5:20:30:4, T = 623 K, in OWGS: CO/H2/H2O/O2 = 0.5:30:20:0.5, T = 493 K
In CO-PROX: CO conv.: 100%, in WGS: CO conv.: 31%, in OWGS: CO conv.: 95%
(1) The addition of O2 greatly promotes the CO conversion. For WGS, the addition of Au in CuO/CeO2 has no promotion on catalytic activation. (2) The presence of Au influences the reduction of CeO2 surface
[180]
ReCu/gadolinium doped ceria
4% Cu, 1% Re
Impregnation method
CO (5%), H2O (10%), N2 balance, a total flow rate= 100 mL·min–1, catalyst (0.15 g), T = 673 K
CO conv.: 93%, the rate of WGS reaction= 61.6 μmol·g–1·s–1
(1) The transfer of electron density between Re, Cu, Ce and Gd contributes to the decrease of catalyst surface. (2) Re helps Cu reduce Ce4+ and produce more Ce3+ on the ceria surface, and leads the catalyst to be more resistant to deactivation
[192]
Tab.6
Fig.14
Catalysts
Composition of catalysts
Preparation methods
Reaction conditions
Catalytic performance
Comments
Ref.
Cu5Mn5-OMC
5 wt-% Cu, 5 wt-% Mn
Solvent evaporation-induced self-assembly method
[NO] = [NH3] = 500 ppm, [O2] = 5 vol-%, Ar balance, a total flow rate= 60 cm3·min–1, GHSV= 36000 h–1, catalyst (0.2 g), T = 523 K
NO conv.: 85%, N2 select.: 90%, N2O concentrations:<50 ppm
(1) Some Cu ions are replaced by Mn ions, causing lattice shrinkage by forming solid solutions. (2) Mn can improve acidity which is good for NH3 adsorption. (3) Mn can provide more adsorption sites for NO, and may be responsible for the adsorption of NH3 and NO
The addition of Ce increases the relative concentration of Cu2+ as well as the Lewis-acid site, which is active for NH3 activation
[209]
Cu–Fe/MWCNT
25 wt-% Cu, 25 wt-% Fe
Facile impregnation method
[NO] = 5 vol-%, [CO] = 10 vol-%, Ar balance, GHSV= 60000 h–1, catalyst (0.05 g), T = 723 K
NO conv.: ~100%, CO conv.: ~50%, Activity: 4.82 kmolNO·s–1·kgcat–1, TOF= 16.3×10–3 s–1
(1) The introduction of Cu–Fe into CNT channels enhances the NO adsorption. (2) Acidic and alkaline sites accelerate NO reduction
[206]
Cu–Fe-ZSM-5
1.48 wt-% Cu, 1.24 wt-% Fe
Solid-state ion exchange method
[NO] = [NH3] = 1000 ppm, He balance, GHSV= 250000 h–1, a total flow rate= 6 L·h–1, catalyst (0.024 g)
50% of NO conv. at 502 K, 100% of NO conv. starting from 569 K
(1) The metal exchange sequence influences the catalytic activation. (2) The addition of Fe to Cu reduces the gathering of Cu particles through the formation Fe–Cu nano compounds. (3) The influence of catalyst acidity is not obvious
[207]
Fe–Cu-ZSM-5
1.36 wt-% Cu, 1.16 wt-% Fe
Solid-state ion exchange method
50% of NO conv. at 507 K, 100% of NO conv. starting from 608 K
[207]
Cr–Cu/ZSM-5
5 wt-% Cu, 3 wt-% Cr
Excess-solution impregnation method
[NO] = 1000 ppm, [NH3] = 1000 ppm, [O2] = 5 vol-%, Ar balance, a total flow Rate= 200 mL·min–1, GHSV= 12000 h–1, catalyst (0.2 g), T = 573 K
NO conv.: 82%
(1) Adding too much Fe has a negative effect because of metal agglomeration and formation of bulk metal particles, resulting in the decrease of active sites. (2) Highly dispersed Lewis-acid sites are produced due to the Lewis nature of Fe ions caused by pyridine adsorption, thus enhancing the adsorption of NH3
[204]
Mn–Cu/ZSM-5
5 wt-% Cu, 3 wt-% Mn
Excess-solution impregnation method
NO conv.: 86%
[204]
Co–Cu/ZSM-5
5 wt-% Cu, 3 wt-% Co
Excess-solution impregnation method
NO conv.: 89%
[204]
Fe–Cu/ZSM-5
5 wt-% Cu, 3 wt-% Fe
Excess-solution impregnation method
NO conv.: 93%
[204]
Fe4–Cu4/ZSM-5
4 wt-% Cu, 4 wt-% Fe
Improved incipient-wetness-impregnation method
[NO] = 1000 ppm, [NH3] = 1000 ppm, [O2] = 3%, N2 balance, a total flow rate= 500 mL·min–1, GHSV= 45000 h–1, catalyst (0.4 g), T = 473 K–648 K
NO conv.: 100%, N2 select.:>95%
(1) Fe can enhance the dispersion of Cu species, produce acidic sites and enhance the adsorption of NH3. (2) Electronic properties of Fe3O4 structures can be changed and accelerates the formation of oxygen vacancies, resulting in high Fe2+/Fe3+ ratio and good activity
[Toluene] = 250 ppm, [NO] = 500 ppm, [O2] = 7 vol-%, N2 balance, total flow= 0.4 l min–1·STP, catalyst (2.5 g), T = 573 K, P = 0.1 MPa, retention time= 4.48×10–5 h–1
NO conv.: 83%, Toluene conv.: 98%
(1) The change of pore structure in Cu–Co/Al2O3 enhances the activity in the reduction of NO with toluene. (2) Toluene conversion is reduced in the presence of NO due to the competitive reaction of O2-toluene-NO
[211]
CuCo/DFS
12.4 wt-% Cu, 8.3 wt-% Co
Wet impregnation method
[NO] = 1200 ppm, [CO] = 1200 ppm, Ar balance, T = 423 K
NO conv.: ~100%, CO conv.: ~100%
The interaction of metal and support is beneficial to the formation of CuCo2O4, Cu1.5Mn1.5O4 and CuO which are responsible for increasing activity
[210]
CuMn/DFS
13.5 wt-% Cu, 10.2 wt-% Mn
Wet impregnation method
NO conv.: ~90%, CO conv.: ~96%
[210]
Cu–Zn/γ-Al2O3
3 wt-% Cu, Cu/Zn molar ratio= 2:1
Chemical reduction method by a liquid polyol solution
[NO] = 400 ppm, [CO] = 200 ppm, [O2] = 6 vol-%, He balance, the total flow rate= 650 mL·min–1, GHSV= 2.4×104 h–1, T = 473 K, P = 0.1 MPa
NO conv.: 100%, CO conv.: 100% (reduction temperature: 413 K, reduction time: 313 K)
The presence of Zn promotes the dispersion of Cu particles, and enhances the redox properties of CuO
[212]
Cu–Ag/mordenite
1.5 wt-% Cu, 1.5 wt-% Ag
Conventional ion exchange method
[NO] = 650 ppm, [C3H6] = 550 ppm, [O2] = 2 vol-%, [CO] = 0.4 vol-%, N2 balance, a total gas flow of 100 mL·min–1, catalyst (0.03 g)
NO conv.: 67%
(1) The CuO formed by the migration of Cu on the surface causes catalyst deactivation. (2) Cu+ and Cu2+ can both adsorb NO, and Ag can promote Cu+/Cu2+ redox cycle
[213]
Tab.7
Fig.15
Catalysts
Composition of catalysts
Preparation methods
Reaction conditions
Catalytic performance
Comments
Ref.
Cu–Ni/Ac
20 wt-% CuO+NiO, Cu/Ni molar ratio= 2:1
Wetness impregnation method
CO/H2O/N2 molar ratio= 4.5%:30.5%:65%, catalyst (0.25 g), T = 623 K
CO conv.: 95%
The size of the catalyst plays a more important role rather than Cu/Ni content
[185]
Cu–Ni/AC
62.7 wt-% Cu, Cu/Ni molar ratio= 1.56:1
Wetness impregnation method
CO/H2O molar ratio= 4.5%:30.6%, N2 balance, GHSV= 4000 h–1, catalyst (0.25 g), T = 623 K
CO conv.: 82.5%
Cu remains in Cu0 during the reaction and the CuNi alloy formation inhibits methane production
[188]
Ni–Cu/SiO2
10 wt-% Ni–Cu, Ni/Cu molar ratio= 5:5
In situ self-assembled core-shell precursor method
CO/H2O molar ratio= 5%:25%, He balance, the total flow rate= 50 mL·min–1, GHSV= 68000 h–1, catalyst (0.05 g), T = 673 K
CO conv.: 78.9%, H2 yield: 45%, TOF= 0.002 s–1
The highly dispersed NiCu alloy can promote the CO adsorption and activate hydroxyl on the SiO2 surface
In situ self-assembled core-shell precursor method
CO conv.: 96.8%, H2 yield: 53%, TOF= 0.004 s–1
OA can promote metal dispersion and enhance the interaction between metal and support
[187]
Cu–Ni/SiO2
–
Thermal decomposition precursor
H2O/CO= 4:1, GHSV= 3600 h–1, catalyst (1.0 g), T = 573 K, P = 0.1 MPa
CO conv.: 97.83%, CO2 select.: 98.64%
This preparation method contributes to the high dispersion of CuO and NiO
[194]
Cu–Ni/γ-Al2O3
10 wt-% Cu, 10 wt-% Ni
Co-precipitation method
H2 (60 vol-%), CO (1 vol-%), O2 (1 vol-%), He balance, GHSV= 60000 h–1, T = 473 K
Without H2O and CO2, CO conv.: 2.91 mmolCO·s–1·kgcat–1, with 10 vol-% H2O: 3.58 mmolCO·s–1·kgcat–1, with 10 vol-% CO2:2.42 mmolCO·s–1·kgcat–1, with 10 vol-% H2O and 10 vol-% CO2: 2.51 mmolCO·s–1·kgcat–1
(1) The addition of H2O has a positive effect on CO conversion while the addition of CO2 has a negative effect. (2) CO conversion is in the order of Cu–Mn/Al2O3>Cu–Ni/Al2O3>Cu/Al2O3>Ni/Al2O3>Mn/Al2O3>Al2O3. (3) The formation of CuMn2O4 contributes to the high dispersion of Cu and Mn, resulting in high CO conversion
[193]
Cu–Mn/γ-Al2O3
10 wt-% Cu, 10 wt-% Mn
Co-precipitation method
H2 (60 vol-%), CO (1 vol-%), O2 (1 vol-%), He balance, GHSV= 60000 h–1, T = 473 K
Without H2O and CO2, CO conv.: 3.32 mmolCO·s–1·kgcat–1, with 10 vol-% H2O: 3.85 mmolCO·s–1·kgcat–1, with 10 vol-% CO2: 2.66 mmolCO·s–1·kgcat–1, with 10 vol-% H2O and 10 vol-% CO2: 3.11 mmolCO·s–1·kgcat–1
[193]
Ce0.7Cu0.1Fe0.2O2−δ
Ce/Cu/Fe molar ratio= 0.7:0.1:0.2
Sonochemical method
CO (2 vol-%), N2 balance, total gas flow rate= 100 mL·min–1, The flow rate of water vapor= 55 mL·min–1, GHSV= 48000 h–1, P = 0.1 MPa
CO conv.: 100%, H2 select.: 100%
Compared to Cu–Ni/CeO2, the activity of Cu–Fe/CeO2 is lower because Fe is more easily to be oxidized under reaction conditions
[191]
Ce0.75Cu0.1Ni0.15O2−δ
Ce/Cu/Ni molar ratio= 0.75:0.1:0.15
Cu0.3Fe0.7Ox
Cu/Fe molar ratio= 3:7
Aerosol-spray self-assembly method
2.2% CO/N2 stream (56 cm3·min–1), CO/H2O feed ratio= 1:7, GHSV= 42000 cm3·g–1·h–1, catalyst (20 mg), T = 523 K, P = 0.1 MPa, t = 140 h
Rate= 1.46×10–6 mol·m–2·s–1, TOF= 0.047 s-1, CO conv.: 50%
(1) The addition of Fe can promote the dispersion of Cu0 and enhance the adsorption of CO and CO2. (2) The addition of Al enhances the durability of the catalyst
[190]
Cu0.3Fe0.6Al0.1Ox
Cu/Fe/Al molar ratio= 3:6:1
Aerosol-spray self-assembly method
Rate= 3.98×10–6 mol·m–2·s–1, TOF= 0.136 s–1, CO conv.: 85%
[190]
CuPd/CeO2
30 wt-% Cu, 1 wt-% Pd
Incipient wetness impregnation method
CO (4 vol-%), CO2 (10 vol-%), air (2 vol-%), Ar (26 vol-%), H2 balance, H2O/CO molar ratio= 10:1
CO conv.: 77%
H2 prefers to be adsorbed and dissociated on Pd site, and H2 spillovers to CuO site, resulting in the congregation of reduced Cu accompanied with water desorption
[183]
Pd–Cu/CeO2
5 wt-% Cu, 1 wt-% Pd
Incipient wetness impregnation method
CO/H2O/CO2/H2/Air= 9.7%:22.8%:6.3%:37.9%:6.9% (1.4% O2), argon balance, a total flow rate of 132.5 mL·min–1, GHSV= 64400 h–1 (dry), catalyst (0.15 g), T = 533 K
H2 production rates: 122 μmol·g–1·s–1
Compared with Pt in Pt-Cu/CeO2, the Pd in Pd–Cu/CeO2 is more surrounded by Cu and the interaction between Cu and Pd is stronger
[184]
Pt–Cu/CeO2
5 wt-% Cu, 1 wt-% Pt
Incipient wetness impregnation method
H2 production rates: 160 μmol·g–1·s–1
[184]
Pt–Cu/ZnO/Al2O3
Cu/Zn molar ratio= 1:1, 0.05 wt-% Pt, 10 mol-% Al
Co-precipitation methods
CO/H2O/H2/CO2/N2 = 0.77:2.2:4.46:0.57:30, GHSV= 4800 mL·h–1·gcat–1, catalyst (0.05 g), T = 523 K
CO conv.: 78%, TOF=1.95×10–2 s–1
Pt promotes the H2 spillover from Pt to Cu to prohibit Cu from sintering and accelerates the reduction-oxidation cycle of Cu0 and Cu+
[182]
Au–Cu/ CeO2
7 wt-% Cu, 1 wt-% Au
Incipient wetness impregnation method
A total flow rate of 200 mL·min–1, balanced to He, GHSV= 12000 h–1, WSV= 1.83 NL min–1·g–1, catalyst (0.1 g), T = 483 K, in WGS. CO/H2O/H2/CO2 = 4:9.4:37.9:3, in CO-PROX: CO/O2/H2 = 4:0.56:37.9, in OWGS: CO/H2O/H2/CO2/O2 = 4:9.4:37.9:3:0.56
In CO-PROX: CO conv.: 36%, in WGS: CO conv.: 1%, in OWGS: CO conv.: 35%,
The catalyst prepared by deposition-precipitation shows higher Au dispersion and oxygen storage capacity than the catalyst prepared by incipient wetness impregnation
[181]
Au–Cu/ CeO2
7 wt-% Cu, 1 wt-% Au
Deposition-precipitation method
in CO-PROX: CO conv.: 37%, in WGS: CO conv.: 3.8%, in OWGS: CO conv.: 40%
[181]
Au–CuO/CeO2
7 wt-% CuO, 1 wt-% Au
Incipient wetness impregnation method
A total flow rate of 200 mL·min–1, He to balance, GHSV= 12000 h–1, WSV= 1.83 NL min–1·g–1, catalyst (0.1 g), in CO-PROX: CO/H2/O2 = 0.5:30:0.5 (in % by vol.), T = 372 K, in WGS: CO/H2O/H2/CO2 = 0.5:20:30:4, T = 623 K, in OWGS: CO/H2/H2O/O2 = 0.5:30:20:0.5, T = 493 K
In CO-PROX: CO conv.: 100%, in WGS: CO conv.: 31%, in OWGS: CO conv.: 95%
(1) The addition of O2 greatly promotes the CO conversion. For WGS, the addition of Au in CuO/CeO2 has no promotion on catalytic activation. (2) The presence of Au influences the reduction of CeO2 surface
[180]
ReCu/gadolinium doped ceria
4% Cu, 1% Re
Impregnation method
CO (5%), H2O (10%), N2 balance, a total flow rate= 100 mL·min–1, catalyst (0.15 g), T = 673 K
CO conv.: 93%, the rate of WGS reaction= 61.6 μmol·g–1·s–1
(1) The transfer of electron density between Re, Cu, Ce and Gd contributes to the decrease of catalyst surface. (2) Re helps Cu reduce Ce4+ and produce more Ce3+ on the ceria surface, and leads the catalyst to be more resistant to deactivation
[192]
Tab.8
Fig.16
Catalysts
Composition of catalysts
Preparation methods
Reaction conditions
Catalytic performance
Comments
Ref.
Ni/Cu nanowires
Cu/Ni molar ratio= 1:2
Liquid phase reduction of Ni and transmetalation reaction of Cu assisted by a magnetic field
Reactant: 4-NP (1×10–4 mol·L–1, 30 mL), reducing agent: NaBH4 (0.05 mol·L–1, 10 mL), at room temperature
K = 0.9118 min–1, 4-NP conv.: 98.65%, the catalyst can be reused for 10 times
Ni has no catalytic activity. The high ratio of corners and edges, and interaction between them enhance the activity
[251]
Cu(0)-Ni(0)-AAPTMS@GO
5 wt-% Cu, Cu/Ni molar ratio= 1:1
Incipient wetness impregnation method
Reactant: 4-NP (5.0 mol·L–1, 30 mL), reducing agent: NaBH4 (60 mg), at room temperature
4-NP conv.: 100%, 4-AP select.: 100%, (in 20 min), the catalyst can be reused for 6 times
Ni is more easily coordinated with the electron-donated N atom of the organic group due to the higher binding capacity than Cu
Kapp= 5.10×10–3 s–1, stably cycle 10 times. The catalyst can be reused for 10 times
The presence of Ni changes the surface electronic structure and the binding energy to the adsorbate is between Cu and Ni
[255]
Fe–Cu/SiO2
3 wt-% Cu, 7 wt-% Fe, Cu/Fe molar ratio= 3:8
Impregnation method
Reactant: P-DB (0.08 mol·L–1, 30 mL), T = 418–453 K, P = 1.3 MPa H2
p-Phenylenediamine select.: 89%
The method of synthesis and the conditions of thermal treatment affect a lot on the catalytic properties of the supported bimetallic Fe–Cu catalysts
[253]
Au/Cu/MgO
0.05 wt-% Cu, Cu/Au molar ratio= 1:1.16
Deposition method of preformed nanocluster beams
Reactant: 4-NP solution (0.06×10–3 mol·L–1), reducing agent: NaBH4 solution 2.5×10–3 mol·L–1), at room temperature
K = 3.49×104 min−1·mol−1, 8.9 (6.6) times higher than the Au-rich (Cu-rich) clusters, 25 times higher than that produced by traditional impregnation method
The Au/Cu alloy NPs shows higher catalytic activity either than rich Au or rich Cu clusters maybe because Au and Cu atoms are randomly located in clusters without chemical ordering, which could be interpreted that there are more Cu/Au sites on the surface to adsorb 4-NPA
[250]
Cu–Au
Cu/Au volume ratio= 99.5:0.5
Co-electrodeposition method
Reactant: 4-NP (1 mmol·L–1), reducing agent: NaBH4 (0.1 mol·L–1), a total volume of 30 mL, T = (293±2) K
k = 27.3 s−1·g−1
The incorporation of Au increases the crystallite size of Cu2O, decreases the size of Cu, and prevents Cu2O from further oxidation
[249]
Cu/Ru/MWCNT
10 wt-% Cu, Cu/Ru molar ratio= 15.78:1
In situ reduction method
Reactant: 4-BTN (1 mmol), reducing agent: NaBH4, anhydrous CoCl2 (0.5 mmol), at room temperature
4-BTN conv.: 100%, 4-bromoaniline select.: 100%, the catalyst can be reused for 5 times
(1) Ru sites are responsible for the dissociative activation of H2 and Cu+ sites contribute on adsorption-activation of C=O bond. (2) NaBH4 is a valid hydrogen source compared to H2, hydrated hydrazine, formic acid and acetic acid
(1) The catalyst supported on ginger rhizome powder exhibits excellent reusability and stability. (2) The catalysts own excellent absorbance of metal ions, surface distribution of nanoparticles, outstanding reusability and stability
Reactant: 4-NP, reducing agent: NaBH4, a total volume of 30 mL, stirring at 800 r?min–1
k(Cu/Pd) = 2.4×10–4 s–1, k(Cu/Au) = 1.4×10–3?s–1, k(Cu/Ag) = 1.6×10–2 s–1, the performance is greatly enhanced with the small amount of CuSO4, and k(Cu/Ag) = 8.5×10–2 s–1 (5.1 min–1)
(1) The presence of Ag forms a network of bulk microcrystals and narrow nanowires, causing many hot pots, while the presence of Au forms large dendrites, reducing hot spots. (2) The localised change in the electronic structure of Cu/Ag contributes to the electron transfer from Cu to Ag and increases the electron density of Ag, and further enhances the adsorption of nitro group
[238]
Cu/Au
Cu/Au molar ratio= 35:65
Electrodeposition method
Reactant: 4-NP, reducing agent: NaBH4, a total volume of 30 mL, stirring at 800 r?min–1
[238]
Cu/Pd
Cu/Pd molar ratio= 56:44
Electrodeposition method
Reactant: 4-NP, reducing agent: NaBH4, a total volume of 30 mL, stirring at 800 r?min–1
[238]
AgCu
–
Two simultaneous replacement method to prepare dendrites in one step
Reactant: 4-NP solution (7×10–5 mol?L–1, 50 mL), reducing agent: NaBH4 solution (0.2 mol?L–1, 3.6 mL), at room temperature
CuPd catalyst has been proved to be the most active catalyst, and the order of activity is as follows: CuPd (k = 193×10–3 mmol·g–1·s–1)>CuPt>CuAu>Cu>Ag1Cu1 >Ag3Cu1 >AuPd>Ag1Cu3 >AgPd>Ag (k = 1.75×10–3 mmol·g–1·s–1)
(1) AgCu exhibited normal dendrites, CuAu dendrites were short with symmetric branches, the CuPd dendrites had longer trunks but irregular branches, and the CuPt dendrites consisted of randomly aggregated nanoparticles. (2) The formation of different dendritic structures results in the various Cu loading and distinct performance
[236]
CuAu
–
Two simultaneous replacement method to prepare dendrites in one step
[236]
CuPt
–
Two simultaneous replacement method to prepare dendrites in one step
[236]
CuPd
–
Two simultaneous replacement method to prepare dendrites in one step
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