Layered alkali titanates (A2TinO2n+1): possible uses for energy/environment issues

doi:10.1007/s11708-021-0776-6

Frontiers in Energy

2021, Vol. 15

Issue (3): 631-655 https://doi.org/10.1007/s11708-021-0776-6

本期目录

Layered alkali titanates (A₂Ti_nO₂_n₊₁): possible uses for energy/environment issues

Taya (Ko) SAOTHAYANUN¹, Thipwipa (Tip) SIRINAKORN², Makoto OGAWA¹(

)

¹. School of Energy Science and Engineering, Vidyasirimedhi Institute of Science and Technology (VISTEC), Wangchan, Rayong 21210, Thailand
². School of Molecular Science and Engineering, Vidyasirimedhi Institute of Science and Technology (VISTEC), Wangchan, Rayong 21210, Thailand

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Abstract：

Uses of layered alkali titanates (A₂Ti_nO₂_n₊₁; Na₂Ti₃O₇, K₂Ti₄O₉, and Cs₂Ti₅O₁₁) for energy and environmental issues are summarized. Layered alkali titanates of various structural types and compositions are regarded as a class of nanostructured materials based on titanium oxide frameworks. If compared with commonly known titanium dioxides (anatase and rutile), materials design based on layered alkali titanates is quite versatile due to the unique structure (nanosheet) and morphological characters (anisotropic particle shape). Recent development of various synthetic methods (solid-state reaction, flux method, and hydrothermal reaction) for controlling the particle shape and size of layered alkali titanates are discussed. The ion exchange ability of layered alkali titanate is used for the collection of metal ions from water as well as a way of their functionalization. These possible materials design made layered alkali titanates promising for energy (including catalysis, photocatalysts, and battery) and environmental (metal ion concentration from aqueous environments) applications.

Key words： layered alkali titanates photocatalysis hydrogen evdution metal ions collection

收稿日期: 2021-02-09 出版日期: 2021-10-09

Corresponding Author(s): Makoto OGAWA

引用本文:

. [J]. Frontiers in Energy, 2021, 15(3): 631-655.
Taya (Ko) SAOTHAYANUN, Thipwipa (Tip) SIRINAKORN, Makoto OGAWA. Layered alkali titanates (A₂Ti_nO₂_n₊₁): possible uses for energy/environment issues. Front. Energy, 2021, 15(3): 631-655.

链接本文:

https://academic.hep.com.cn/fie/CN/10.1007/s11708-021-0776-6
https://academic.hep.com.cn/fie/CN/Y2021/V15/I3/631

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Photocatalytic H₂ evolution reaction
Layered alkali titanates or its derivative	Starting materials	Synthetic method	Photocatalytic conditions	Light source	Co-catalysts	Efficiency/(µmol·(h·g)^?1)	Ref.
Na₂Ti₃O₇	–	Solid-state reaction	Methanol-water (20%, volume fraction)	500 W Xe	–	5.8	[93]
Na₂Ti₃O₇	–	Solid-state reaction	Methanol-water (20%, volume fraction)	500 W Xe	Pt	38
H₂Ti₃O₇	Na₂Ti₃O₇	Proton exchange reaction	Methanol-water (20%, volume fraction)	500 W Xe	–	3.8
H₂Ti₃O₇	Na₂Ti₃O₇	Proton exchange reaction	Methanol-water (20%, volume fraction)	500 W Xe	Pt	11
K₂Ti₂O₅	–	Solid-state reaction	Methanol-water (20%, volume fraction)	500 W Xe	–	41.6
K₂Ti₂O₅	–	Solid-state reaction	Methanol-water (20%, volume fraction)	500 W Xe	Pt	69.4
H₂Ti₂O₅	K₂Ti₂O₅	Proton exchange reaction	Methanol-water (20%, volume fraction)	500 W Xe	–	66.8
H₂Ti₂O₅	K₂Ti₂O₅	Proton exchange reaction	Methanol-water (20%, volume fraction)	500 W Xe	Pt	83.8
K₂Ti₄O₉	–	Solid-state reaction	Methanol-water (20%, volume fraction)	500 W Xe	–	7
K₂Ti₄O₉	–	Solid-state reaction	Methanol-water (20%, volume fraction)	500 W Xe	Pt	9.6
H₂Ti₄O₉	K₂Ti₄O₉	Proton exchange reaction	Methanol-water (20%, volume fraction)	500 W Xe	–	6.4
H₂Ti₄O₉	K₂Ti₄O₉	Proton exchange reaction	Methanol-water (20%, volume fraction)	500 W Xe	Pt	27.6
K₂Ti₆O₁₃	–	Solid-state reaction	Methanol-water (20%, volume fraction)	500 W Xe	–	8.4
K₂Ti₆O₁₃	–	Solid-state reaction	Methanol-water (20%, volume fraction)	500 W Xe	Pt	121
H₂Ti₆O₁₃	K₂Ti₆O₁₃	Proton exchange reaction	Methanol-water (20%, volume fraction)	500 W Xe	–	30.2
H₂Ti₆O₁₃	K₂Ti₆O₁₃	Proton exchange reaction	Methanol-water (20%, volume fraction)	500 W Xe	Pt	166
Cs₂Ti₂O₅	-	Solid-state reaction	Methanol-water (3%, volume fraction)	400 W high-pressure Hg	–	500	[94]
H₂Ti₂O₅	Cs₂Ti₂O₅	Proton exchange reaction	Methanol-water (3%, volume fraction)	400 W high-pressure Hg	–	852
H₂Ti₂O₅	Cs₂Ti₂O₅	Proton exchange reaction	Methanol-water (3%, volume fraction)	400 W high-pressure Hg	Pt	2510
Cs₂Ti₅O₁₁	–	Solid-state reaction	Methanol-water (3%, volume fraction)	400 W high-pressure Hg	–	90
Cs₂Ti₆O₁₃	–	Solid-state reaction	Methanol-water (3%, volume fraction)	400 W high-pressure Hg	–	38
K₂Ti₄O₉	–	Solid-state reaction	Methanol-water (20%, volume fraction)	300 W Xe	–	40	[13]
K₂Ti₄O₉	–	Solid-state reaction	Methanol-water (20%, volume fraction)	300 W Xe	Pt	2210
H₂Ti₄O₉	–	Proton exchange reaction	Methanol-water (20%, volume fraction)	300 W Xe	–	290
H₂Ti₄O₉	–	Proton exchange reaction	Methanol-water (20%, volume fraction)	300 W Xe	Pt	2520
TBA₂-Ti₄O₉	H₂Ti₄O₉	Exfoliation	Methanol-water (20%, volume fraction)	300 W Xe	–	140
TBA₂-Ti₄O₉	H₂Ti₄O₉	Exfoliation	Methanol-water (20%, volume fraction)	300 W Xe	Pt	4050
Sn(II)-K₂Ti₄O₉	K₂Ti₄O₉	Ion exchange reaction	Methanol-water (10%, volume fraction)	300 W Xe	Pt	115	[96]
Sn(II)-K₂Ti₂O₅	K₂Ti₂O₅	Ion exchange reaction	Methanol-water (10%, volume fraction)	300 W Xe	Pt	25
Sn(II)-Cs₂Ti₆O₁₃	Cs₂Ti₆O₁₃	Ion exchange reaction	Methanol-water (10%, volume fraction)	300 W Xe	Pt	35
Sn(II)-K₂Ti₆O₁₃	K₂Ti₆O₁₃	Ion exchange reaction	Methanol-water (19%, volume fraction)	300 W Xe	Pt	250	[122]
Li_2–_x H_xTi₃O₇	–	Alkaline hydrothermal and ion exchange reaction	Methanol	30 W UV	Pt	2910	[97]
Na_2–_x H_xTi₃O₇	–	Alkaline hydrothermal and ion exchange reaction	Methanol	30 W UV	Pt	2700
K_2–_x H_xTi₃O₇	–	Alkaline hydrothermal and ion exchange reaction	Methanol	30 W UV	Pt	3630
Cs_2–_x H_xTi₃O₇	–	Alkaline hydrothermal and ion exchange reaction	Methanol	30 W UV	Pt	2280
K₂Ti₆O₁₃ fibers	–	Flux synthesis and heat treatment	Methanol-water (2%, volume fraction)	250 W Hg	–	298	[100]
K₂Ti₆O₁₃ fibers	–	Flux synthesis	Water vapor	300 W Xe	Rh	18	[101]
[Ti_3–_xRh_xO₇]^2? nanosheets	–	Solid-state reaction and exfoliation	Triethylamine-water (pH 11)	500 W Xe (>220 nm)	–	1040	[102]
[Ti_3–_xRh_xO₇]^2? nanosheets				500 W Xe (>340 nm)	–	302
[Ti₃O₇]^2? nanosheets				500 W Xe (>220 nm)	Rh	1970
H₂Y_xTi_(2–_x₎O₅·H₂O/anatase/rutile	–	Microwave-assisted alkaline hydrothermal method in the presence of Y salt and proton exchange reaction	Methanol-water	Hg-Xe lamp	–	72	[103]
					Ni	6660
					Cu	11660
					Co	5280
Anatase TiO₂/K₂Ti₄O₉	K₂Ti₄O₉	Hydrothermal treatment in TBA, NH₄F solution	Methanol-water (5%, volume fraction)	150 W Xe (>450 nm)	Ni	0.12	[123]
WO₃/H₂Ti₃O₇	H₂Ti₃O₇	Microwave-assisted hydrothermal method	2-propanol-water (50%, volume fraction)	UV LED (365 nm)	Rh	4680	[113]
WO₃/H₂Ti₃O₇	H₂Ti₃O₇	Microwave-assisted hydrothermal method	2-propanol-water (50%, volume fraction)	Vis LED (450 nm)	Rh	1740	[113]
Cr₂O₃/titanate nanosheets	H₂Ti₃O₇	Alkaline hydrothermal treatment in the presence of Cr source and proton exchange reaction	Triethanolamine-water (10%, volume fraction)	300 W Xe (>420 nm)	Pt	473	[124]
H₂Ti₂O₄(OH)₂	–	Alkaline hydrothermal treatment	Na₂S/Na₃SO₃-water	300 W Xe	–	195	[125]
GQDs/H₂Ti₂O₄(OH)₂	H₂Ti₂O₄(OH)₂ nanotubes	Solvothermal treatment of H₂Ti₂O₄(OH)₂ with citric acid in DMF			–	290
CdS/GQDs/H₂Ti₂O₄(OH)₂	GQDs/H₂Ti₂O₄(OH)₂	Ion exchange with Cd(II) followed by sulfurization			–	530
H₂Ti₃O₇ nanobelts	Na₂Ti₃O₇	Alkaline hydrothermal treatment and proton exchange reaction	Methanol-water (18%, volume fraction)	Solar simulator (AM 1.5 G,>300 nm)	Pt	n/d	[109]
Mesoporous TiO₂-B nanobelts	H₂Ti₃O₇	Heat treatment in air			Pt	9375
Anatase TiO₂ nanobelts	H₂Ti₃O₇	Heat treatment in air			Pt	4030
Octahedral Anatase Particles (OAPs)	K₂Ti₈O₁₇	Hydrothermal treatment of K₂Ti₈O₁₇	Methanol-water (50%, volume fraction)	400 W High pressure Hg	Pt	4320	[121]
Anatase TiO₂ nanorods	H₂Ti₃O₇ nanotubes	Heat treatment in air	Ethanol-water (10%, volume fraction)	100 W UV LED (365 nm)	Au	14400	[126]
Anatase TiO₂ nanorods	H₂Ti₃O₇ nanotubes	Heat treatment in air	Glycerol-water (10%, volume fraction)	100 W UV LED (365 nm)	Au	29200	[126]
Anatase TiO₂ nanorods	H₂Ti₃O₇ nanotubes	Heat treatment	Ethanol-water (10%, volume fraction)	100 W UV LED (365 nm)	Pd	30000	[110]
					Au	8700
					Pd-Au	39000
N-doped defected-anatase TiO₂	H₂Ti₂O₅·H₂O	Heat treatment of DMF/H₂Ti₂O₅·H₂O in air	50%, volume fraction methanol-water	Solar simulator	–	1035	[105]
Rutile TiO₂ nanobundles	H₂Ti₅O₁₁·3H₂O	HNO₃ treatment of layered titanic acid under reflux	Triethanolamine-water	300 W Xe arc (0.38 W/cm²)	Pt	8048 (3.1 times over Degussa P25)	[127]
Ni(0)-Anatase TiO₂/Titanate	H₂Ti₄O₉·H₂O	Precipitation of Ni(OH)₂ onto H₂Ti₄O₉·H₂O and thermalreduction in innert atmosphere	2-propanol-water (1%, volume fraction)	100 W Hg	–	1040	[128]
NiTiO₃/Anatase TiO₂ nanotube	H₂Ti_nO₂_n₊₁ nanotubes	Adsorption of Ni(II) and heat treatment in air	Methanol-water (10%, volume fraction)	300 W Xe	–	680	[129]
Cu(OH)₂-Ni(OH)₂/Anatase TiO₂ nanorods	H₂Ti₃O₇ nanotubes	Heat treatment of H₂Ti₃O₇ and co-deposition of copper and nickel hydroxides	Ethanol-water (20%, volume fraction)	100 W UV LED (365 nm)	–	26600	[130]
Anatase TiO₂ microspheres	H₂Ti₄O₉ nanotube	Hydrothermal treatment of H₂Ti₄O₉ in HF/urea solution	tri-ammonium phosphate-water	1000 W Hg	–	31250 (2.5 fold greater than H₂Ti₄O₉ nanotube)	[117]
Anatase/K_2–_x H_xTi_nO₂_n₊₁, n = 6, 8	–	Alkaline hydrothermal and proton exchange reaction	0.3 mol/L NH₃BH₃/H₂O+ 40°C	100 W UV LED (365 nm)	–	10000	[116]
rGO/Na₂Ti₃O₇	–	Alkaline hydrothermal treatment in the presence of rGO	Ammonia borane-water	Xe lamp (220 mW/cm²)	–	131 mL/(g_cat·min)(2.7 times higher than Na₂Ti₃O₇)	[119]
Fe-Co exchanged titanate nanotubes	Na₂Ti₃O₇	Ion exchange reaction with Fe and Co cations	Triammonium phosphate-water	Sun light (Egypt, latitude 29° N)	–	348200 µmol/(h·g_salt·g_cat)	[118]
Photocatalytic CO₂ reduction
Layered alkali titanates or its derivative	Starting materials	Synthetic method	Photocatalytic conditions	Light source	Co-catalysts	Efficiency	Ref.
Titanate-(Zr)UiO-66	H₂Ti₂O₅.H₂O	Microwave-assisted solvothermal treatment in the presence of Zr and 2‐aminoteraphtalic acid	CO₂-H₂-Water	150 W Xe arc (>325 nm)	–	0.45 (µmol CO/(h·g))	[131]
Anatase-(Zr)UiO-66	H₂Ti₂O₅.H₂O	Heat treatment and microwave-assisted solvothermal treatment	CO₂-H₂-Water	150 W Xe arc (>325 nm)	–	0.85 (µmol CO/(h·g))	[131]
CdS/(Cu(0)-Na_xH_2–_xTi₃O₇)	Na_xH_2–_xTi₃O₇	Adsorption of Cu(II) and heat treatment in inert atmosphere (H₂/N₂), Adsorption of Cd(II), hydrothermal treatment in Na₂S aqueous solution for sulfurization, and heat treatment in inert atmosphere	CO₂-water	450 W Xe (>420 nm)	–	27.5(µl CH₄/ (h·g)), 17(µl C₂H₆/ (h·g)), 10(µl C₃H₈/ (h·g))	[120]
CdS/(Cu(0)-Na_xH_2–_xTi₃O₇)	Na_xH_2–_xTi₃O₇		CO₂-water	450 W Xe (>420 nm)	–	27.5(µl CH₄/ (h·g)), 17(µl C₂H₆/ (h·g)), 10(µl C₃H₈/ (h·g))	[120]
Octahedral Anatase Particles (OAPs)	K₂Ti₈O₁₇	Hydrothermal treatment of K₂Ti₈O₁₇	Acetic acid-water (5%, volume fraction)	400 W High pressure Hg	Pt	1130(µmol CO₂/(h·g)	[121]

Tab.4

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Fig.24

Fig.25

Fig.26

Fig.27

Fig.28

Fig.29

Fig.30

Fig.31

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