Novel materials and techniques for photocatalytic water splitting developed by Professor Kazunari Domen

doi:10.1016/S1872-2067(24)60152-X

Chinese Journal of Catalysis ›› 2025, Vol. 68: 1-50.DOI: 10.1016/S1872-2067(24)60152-X

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Novel materials and techniques for photocatalytic water splitting developed by Professor Kazunari Domen

Yaqiang Wu^a^,^b^,¹, Jianuo Li^a^,¹, Wei-Kean Chong^c^,¹, Zhenhua Pan^d^,^*(), Qian Wang^a^,^e^,^*()

^aGraduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
^bState Key Laboratory of Crystal Materials, Institute of Crystal Materials, Shandong University, Jinan 250100, Shandong, China
^cMultidisciplinary Platform of Advanced Engineering, Department of Chemical Engineering, School of Engineering, Monash University Malaysia, Jalan Lagoon Selatan, 47500 Bandar Sunway, Selangor, Malaysia
^dDepartment of Applied Chemistry, Graduate School of Engineering, University of Hyogo, Himeji, Hyogo 671-2280, Japan
^eInstitute for Advanced Research, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8601, Japan

Received:2024-07-16 Accepted:2024-09-24 Online:2025-01-18 Published:2025-01-02
Contact: * E-mail: wang.qian@material.nagoya-u.ac.jp (Q. Wang), pan@eng.u-hyogo.ac.jp (Z. Pan).
About author:Zhenhua Pan (Associate Professor at Department of Applied Chemistry, Graduation School of Engineering, University of Hyogo, Japan) earned his Ph.D. from the University of Tokyo under the supervision of Prof. Kazunari Domen in 2016. In April 2020, he became an assistant professor in the Katayama Lab at Chuo University. In April 2024, he started his own lab at the University of Hyogo as an associate professor. His research focuses on the development of wide-spectrum-responsive photocatalysts for artificial photosynthesis, the investigation of photochemical processes in photocatalytic reactions, and the creation of scalable photocatalyst panels.
Qian Wang (Associate Professor at Nagoya University, Japan) obtained her PhD in 2014 from the University of Tokyo under the supervision of Professor Kazunari Domen, followed by postdoctoral research at the same institution. In 2018, she was awarded the Marie Sklodowska-Curie Research Fellowship and joined the Reisner Group at the University of Cambridge. Since joining Nagoya University as an Associate Professor in May 2021, she has established her research group focused on developing innovative materials, strategies, and technologies for solar energy storage through artificial photosynthesis, with the goal of producing renewable fuels.
¹Contributed equally to this work.
Dedicated to Prof. K. Domen on the occasion of his 70th birthday.

Abstract

Abstract:

Professor Kazunari Domen at the Shinshu University and the University of Tokyo has pioneered materials and techniques for solar-driven water splitting using photocatalysts, a promising technology for contributing to the construction of a sustainable and carbon-neutral society. In this paper, we summarize his groundbreaking contributions to photocatalytic water splitting and, more broadly, photocatalytic research. We highlight various novel functional photocatalytic materials, including oxides, (oxy)nitrides, and oxysulfides, along with innovative techniques such as cocatalyst engineering and Z-scheme system construction developed by the Domen Group. His team has also pioneered readily accessible and cost-effective photo(electro)chemical device fabrication methods, such as the particle-transfer method and thin-film-transfer method. Furthermore, their research has made significant contributions to understanding the (photo)catalytic mechanisms using advanced characterization techniques. Together with his research team, Professor Domen has set many milestones in the field of photocatalytic overall water splitting, notably demonstrating the first scalable and stable 100 m² solar H₂ production system using only water and sunlight. His work has revealed the potential for practical solar H₂ production from water and sunlight, and highlighted the application of fundamental principles, combined with chemical and materials science tools, to design effective photocatalytic systems. Through this review, we focus on his research and the foundational design principles that can inspire the development of efficient photocatalytic systems for water splitting and solar fuel production. By building on his contributions, we anticipate a significant impact on addressing major global energy challenges.

Key words: Photocatalysis, Water splitting, Solar H₂ production, Solar energy conversion, Artificial photosynthesis

Yaqiang Wu, Jianuo Li, Wei-Kean Chong, Zhenhua Pan, Qian Wang. Novel materials and techniques for photocatalytic water splitting developed by Professor Kazunari Domen[J]. Chinese Journal of Catalysis, 2025, 68: 1-50.

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Approach	Advantage	Challenge	Example	STH	Ref.
Natural photosynthesis	high scalability	low efficiency	plants and algae	typically < 0.5%
Two-step thermochemical reactions	lower reaction temperature compared to direct thermolysis; flexible reoxidation timing, performed at night or as needed	precise control of reaction conditions low efficiency	porous monolithic CeO₂ in an advanced solar-cavity receiver reactor	maximum 0.7% for over 500 cycles	[5]
PV-E	high efficiency simple to optimize use of commercial materials	high cost complex structure relatively low scalability	InGaP/GaAs/GaInNAsSb solar cell + polymer electrolyte membrane (PEM) electrolyzer	maximum 30% for the first 48 hours	[14]
PEC	relative high efficiency simple to optimize utilization of semiconductor-liquid junctions	relative high cost low stability low scalability	RuO₂\|GaAs/GaInAs/GaInP/AlInP\|anatase TiO₂/Rh\|electrolyte	maximum 19% for 2 hours	[9]
Homogenous PC system	bio-mimetic and bio-inspired high activity per active site low cost	organic solvent sacrificial reagent soluble redox mediator low stability	two-electron mixed-valence dirhodium compound, Eosin Y with hydrogenase	—	[10, 11]
Heterogeneous PC system	low cost high scalability simplicity	low efficiency	cocatalyst-modified SrTiO₃:Al	maximum 0.76% for 1600 hours, 100 m²	[15]

Approach	Advantage	Challenge	Example	STH	Ref.
Natural photosynthesis	high scalability	low efficiency	plants and algae	typically < 0.5%
Two-step thermochemical reactions	lower reaction temperature compared to direct thermolysis; flexible reoxidation timing, performed at night or as needed	precise control of reaction conditions low efficiency	porous monolithic CeO₂ in an advanced solar-cavity receiver reactor	maximum 0.7% for over 500 cycles	[5]
PV-E	high efficiency simple to optimize use of commercial materials	high cost complex structure relatively low scalability	InGaP/GaAs/GaInNAsSb solar cell + polymer electrolyte membrane (PEM) electrolyzer	maximum 30% for the first 48 hours	[14]
PEC	relative high efficiency simple to optimize utilization of semiconductor-liquid junctions	relative high cost low stability low scalability	RuO₂\|GaAs/GaInAs/GaInP/AlInP\|anatase TiO₂/Rh\|electrolyte	maximum 19% for 2 hours	[9]
Homogenous PC system	bio-mimetic and bio-inspired high activity per active site low cost	organic solvent sacrificial reagent soluble redox mediator low stability	two-electron mixed-valence dirhodium compound, Eosin Y with hydrogenase	—	[10, 11]
Heterogeneous PC system	low cost high scalability simplicity	low efficiency	cocatalyst-modified SrTiO₃:Al	maximum 0.76% for 1600 hours, 100 m²	[15]

Photocatalyst		Surface modification		Reaction medium		Light source	Gas evolution rate				Efficiency ^a	Duration (stability) ^b		Ref.
Photocatalyst		Surface modification		Reaction medium		Light source	H₂		O₂		Efficiency ^a	Duration (stability) ^b		Ref.
BaTaO₂N:Mg		Na-Rh/Cr₂O₃/IrO₂		water		300 W Xe lamp (λ > 420 nm)	2 μmol/h		1 μmol/h		AQY: 0.08% (420 nm) STH: 0.0004% (0.92 Sun)	30 h (~99%)		[70]
BaTaO₂N		Rh/Cr₂O₃/IrO₂		water		300 W Xe lamp (AM 1.5G)	~0.27 μmol/h		~0.13 μmol/h		AQY: 0.1% (400 nm) STH: 0.0005% (1 Sun)	15 h (~86%)		[71]
CaTaO₂N		RhCrO_y		water		300 W Xe lamp (λ > 300 nm)	~1.3 μmol/h		~0.6 μmol/h		AQY: 0.003% (440 nm)	30 h (~86%)		[72]
CaTaO₂N		Ru/Cr₂O₃/Ir		water		300 W Xe lamp (λ > 420 nm)	4.92 μmol/h		2.12 μmol/h		AQY: 0.45% (420 nm) STH: 0.012% (1 Sun)	20 h (~70%)		[73]
Cs₂La₂Ti₃O₁₀		Ni/NiO		water		450 W mercury lamp	700 μmol/h		340 μmol/h					[49]
Cs_1.5La₂Ti_2.5Nb_0.5O₁₀		Ni/NiO		water		450 W mercury lamp	540 μmol/h		265 μmol/h					[49]
CsLa₂Ti₂NbO₁₀		Ni/NiO		water		450 W mercury lamp	115 μmol/h		50 μmol/h					[49]
Dy₂Ti₂O₇		NiO_x		water		400 W mercury lamp	~160.3 μmol/h		~72.6 μmol/h					[74]
Er₂Ti₂O₇		NiO_x		water		400 W mercury lamp	~419.2 μmol/h		~184.9 μmol/h					[74]
Eu₂Ti₂O₇		NiO_x		water		400 W mercury lamp	~17.8 μmol/h		~6.8 μmol/h					[74]
GaN:Mg		RuO₂		water		450 W mercury lamp	~670 μmol/h		~280 μmol/h			21 h (~99%)		[75]
GaN:ZnO		Rh/Cr₂O₃/IrO₂		water (H₂SO₄, pH 4)		300 W Xe lamp (λ > 420 nm)	14 μmol/h		7.1 μmol/h		STH: 0.0125% (1 Sun)	5 h		[76]
GaN:ZnO		RuO₂		water (H₂SO₄, pH 3)		450 W mercury lamp (visible)	~58 μmol/h		~30 μmol/h		AQY: 0.14% (300-480 nm)	15 h (~98%)		[16]
GaN:ZnO		Rh/Cr₂O₃/ Mn₃O₄		water		300 W Xe lamp (λ > 420 nm)	~11.2 μmol/h		~4.9 μmol/h			12 h		[77]
GaN:ZnO		Rh/Cr₂O₃ (ads.)		water		450 W mercury lamp (λ > 400 nm)	426 μmol/h		213 μmol/h			8 h (~99%)		[78]
(Ga_1‒_xZn_x)(N_1‒_xO_x)		Rh-Cr		water (H₂SO₄, pH 4.5)		450 W mercury lamp	~320 μmol/h		~150 μmol/h		AQY: 2.5% (430 nm)	35 h (~97%)		[17]
(Ga_1‒_xZn_x)(N_1‒_xO_x)		RuO₂		water (H₂SO₄, pH 3)		450 W mercury lamp	58 μmol/h		29 μmol/h		AQY: 0.23% (420 nm)			[16]
(Ga_1‒_xZn_x)(N_1‒_xO_x)		Rh/Cr₂O₃		water		450 W mercury lamp (λ > 400 nm)	~175.1 μmol/h		~139 μmol/h			4 h		[79]
(Ga_1‒_xZn_x)(N_1‒_xO_x)		Rh_2‒_yCr_yO₃/SiO₂		water		300 W Xe lamp (λ > 300 nm)	~130.7 μmol/h		~57.7 μmol/h			7 h		[80]
Gd₂Ti₂O₇		NiO_x		water		400 W mercury lamp	~446.6 μmol/h		~228.8 μmol/h					[74]
β-Ge₃N₄		RuO₂		water (H₂SO₄, pH 0)		450 W mercury lamp	467 μmol/h		~233 μmol/h			25 h		[81]
β-Ge₃N₄ (NH₃)		RuO₂		water		450 W mercury lamp	1100 μmol/h		550 μmol/h		AQY: 7.0% (300 nm)	5 h		[82]
Ho₂Ti₂O₇		NiO_x		water		400 W mercury lamp	~564.4 μmol/h		~253.4 μmol/h					[74]
K₂La₂Ti₃O₁₀		Ni/NiO		water (0.1 mol/L KOH)		450 W mercury lamp	444 μmol/h		221 μmol/h			10 h (~99%)		[57]
K₂La₂Ti₃O₁₀		Cr/Ni		water (0.1 mol/L KOH)		450 W mercury lamp	885 μmol/h		442 μmol/h			124 h (~40%)		[83]
K₄Nb₆O₁₇		Ni/NiO		water		450 W mercury lamp	63 μmol/h		31 μmol/h		AQY: 3.5% (330 nm)	50 h (~86%)		[55]
K₄Nb₆O₁₇		NiO		water (pH 9.7)		450 W mercury lamp	124 μmol/h		62 μmol/h		AQY: 5.2% (330 nm)	5 h		[84]
K₂Rb₂Nb₆O₁₇		NiO		water (pH 9.7)		450 W mercury lamp	78 μmol/h		39 μmol/h		AQY: 3.3% (330 nm)	5 h		[84]
LaMg_1/3Ta_2/3O₂N		TiOXH/SiOXH/ RhCrO_y		water		300 W Xe lamp (λ > 300 nm)	~3.6 μmol/h		~1.8 μmol/h		AQY: 0.3% (440 nm)	22 h (~98%)		[85]
LaMg_1/3Ta_2/3O₂N		TiO₂/RhCrO_y		water		300 W Xe lamp (λ > 300 nm)	~1.9 μmol/h		~0.9 μmol/h			5 h		[86]
LaMg_1/3Ta_2/3O₂N		RhCrO_y/SiO₂/ TiO₂		water		300 W Xe lamp (λ > 300 nm)	22 μmol/h		11 μmol/h		AQY: 0.18% (430 nm)	27 h (~99%)		[87]
Lu₂Ti₂O₇		NiO_x		water		400 W mercury lamp	~58.9 μmol/h		~21.9 μmol/h					[74]
Rb₂La₂Ti₃O₁₀		Ni/NiO		water (0.1 mol/L RbOH)		450 W mercury lamp	869 μmol/h		430 μmol/h			30 h (~87%)		[49]
Rb_1.5La₂Ti_2.5Nb_0.5O₁₀		Ni/NiO		water (0.1 mol/L RbOH)		450 W mercury lamp	725 μmol/h		358 μmol/h					[49]
RbLa₂Ti₂NbO₁₀		Ni/NiO		water (0.1 mol/L RbOH)		450 W mercury lamp	79 μmol/h		30 μmol/h					[49]
Rb₄Nb₆O₁₇	NiO		water (pH 9.7)		450 W mercury lamp		228 μmol/h	110 μmol/h		AQY: 10.0% (330 nm)		30 h (~91%)	[84]
SrTaO₂N	CrO_y/Ru/IrO₂		water (NaOH, pH 8)		300 W Xe lamp (λ > 420 nm)		9.1 μmol/h	3.0 μmol/h		AQY: 0.34% (420 nm) STH: ~0.0055% (1 Sun)		18 h (~65%)	[88]
SrTiO₃	NiO_x		water vapor		450 W mercury lamp		4.4 μL/h	2.2 μL/h					[24]
SrTiO₃	Ni/NiO		water		450 W mercury lamp		24.4 μmol/h	10.6 μmol/h				60 h (~95%)	[27]
SrTiO₃	NiO_x		water (5 mol/L OH^-)		450 W mercury lamp		24 μmol/h	~12 μmol/h					[25]
SrTiO₃	Rh₂O₃/Cr₂O₃		water		450 W mercury lamp		~400 μmol/h	~200 μmol/h				5 h	[38]
SrTiO₃:Al	Rh_2‒_yCr_yO₃		water		300 W Xe lamp (λ > 300 nm)		550 μmol/h	280 μmol/h		AQY: 30% (360 nm)		5 h	[41]
SrTiO₃:Al	MoO_x/RhCrO_y		water		300 W Xe lamp (300-500 nm)		~1.8 mmol/h	~0.9 mmol/h		AQY: 60% (365 nm)		16 h (~91%)	[42]
SrTiO₃:Al	Rh/Cr₂O₃/ CoOOH		water		300 W Xe lamp (full arc)		3.54 mmol/h	1.78 mmol/h		EQE: 95.7% (350 nm) STH: 0.65% (1 Sun)		12.5 (~94%)	[46]
SrTiO₃:Al	RhCrO_y/CoO_y		water vapor		20 mW UV LED (365 nm)		~0.9 μmol/h	~0.4 μmol/h		AQY: 0.86% (365 nm)		6 h	[89]
SrTiO₃:Al [100 m² panel]	Rh_2‒_yCr_yO₃/ CoO_x		water		Natural sunlight		oxyhydrogen: 568 mL/min			STH: 0.76%		1600 h (~79%)	[15]
SrTiO₃:Ga	Rh₂O₃/Cr₂O₃		water		450 W mercury lamp		~4.3 mmol/h	~2.2 mmol/h				2 h	[38]
SrTiO₃:Ga, La	Rh₂O₃/Cr₂O₃		water		450 W mercury lamp		~1200 μmol/h	~600 μmol/h				2 h	[38]
SrTiO₃:La	Rh₂O₃/Cr₂O₃		water		450 W mercury lamp		~100 μmol/h	~50 μmol/h				5 h	[38]
SrTiO₃:Na	Rh₂O₃/Cr₂O₃		water		450 W mercury lamp		~10.1 mmol/h	~5.2 mmol/h				1.5 h	[38]
SrTiO₃:Na, Ta	Rh₂O₃/Cr₂O₃		water		450 W mercury lamp		~400 μmol/h	~200 μmol/h				5 h	[38]
SrTiO₃:Ta	Rh₂O₃/Cr₂O₃		water		450 W mercury lamp		~200 μmol/h	~100 μmol/h				5 h	[38]
Ta₃N₅	Rh/Cr₂O₃		water		300 W Xe lamp (λ > 420 nm)		~10.9 μmol/h	~4.8 μmol/h		AQY: 2.2% (320 nm) STH: 0.014% (1 Sun)		15 h (~90%)	[90]
TaON:Zr	Ru/Cr₂O₃/IrO₂		water (NaOH, pH 8.0)		300 W Xe lamp (λ > 380 nm)		~13.7 μmol/h	~ 6.3 μmol/h		AQY: 0.81% (365 nm) STH: 0.009% (0.8 Sun)		24 h (82%)	[91]
Tm₂Ti₂O₇	NiO_x		water		400 W mercury lamp		~237.0 μmol/h	~106.9 μmol/h					[74]
Yb₂Ti₂O₇	NiO_x		water		400 W mercury lamp		~198.6 μmol/h	~94.5 μmol/h					[74]
Y₂Ti₂O₅S₂	IrO₂/Rh/Cr₂O₃		water (La₂O₃, pH 8.5)		300 W Xe lamp (λ > 420 nm)		~6.4 μmol/h	~3.2 μmol/h		AQY: 0.36% (420 nm) STH: 0.007% (1 Sun)		20 h (~81%)	[92]
ZrO₂:TaON	IrO₂/Cr₂O₃/ RuO_x		water		450 W mercury lamp (visible)		~3.0 μmol/h	~1.4 μmol/h		AQY: ~0.1% (420 nm)		16 h	[93]
(Zn₁₊_xGe)(N₂O_x)	Rh_2‒_yCr_yO₃		water		300 W Xe lamp (λ > 420 nm)		11.1 μmol/h	5.4 μmol/h		AQY: 0.20% (420 nm)		50 h (~87%)	[94]
(Zn_1.44Ge)(N₂O_0.44)	RuO₂		Water		420 W mercury lamp (visible)		14.2 μmol/h	7.4 μmol/h				10 h (~99%)	[95]
(Zn_1.44Ge)(N₂O_0.44)	Rh_yCr_2‒_yO₃		water		450 W mercury lamp (λ > 400 nm)		~520.6 μmol/h	~262.7 μmol/h		AQY: 2.0% (430 nm)			[96]

Photocatalyst		Surface modification		Reaction medium		Light source	Gas evolution rate				Efficiency ^a	Duration (stability) ^b		Ref.
Photocatalyst		Surface modification		Reaction medium		Light source	H₂		O₂		Efficiency ^a	Duration (stability) ^b		Ref.
BaTaO₂N:Mg		Na-Rh/Cr₂O₃/IrO₂		water		300 W Xe lamp (λ > 420 nm)	2 μmol/h		1 μmol/h		AQY: 0.08% (420 nm) STH: 0.0004% (0.92 Sun)	30 h (~99%)		[70]
BaTaO₂N		Rh/Cr₂O₃/IrO₂		water		300 W Xe lamp (AM 1.5G)	~0.27 μmol/h		~0.13 μmol/h		AQY: 0.1% (400 nm) STH: 0.0005% (1 Sun)	15 h (~86%)		[71]
CaTaO₂N		RhCrO_y		water		300 W Xe lamp (λ > 300 nm)	~1.3 μmol/h		~0.6 μmol/h		AQY: 0.003% (440 nm)	30 h (~86%)		[72]
CaTaO₂N		Ru/Cr₂O₃/Ir		water		300 W Xe lamp (λ > 420 nm)	4.92 μmol/h		2.12 μmol/h		AQY: 0.45% (420 nm) STH: 0.012% (1 Sun)	20 h (~70%)		[73]
Cs₂La₂Ti₃O₁₀		Ni/NiO		water		450 W mercury lamp	700 μmol/h		340 μmol/h					[49]
Cs_1.5La₂Ti_2.5Nb_0.5O₁₀		Ni/NiO		water		450 W mercury lamp	540 μmol/h		265 μmol/h					[49]
CsLa₂Ti₂NbO₁₀		Ni/NiO		water		450 W mercury lamp	115 μmol/h		50 μmol/h					[49]
Dy₂Ti₂O₇		NiO_x		water		400 W mercury lamp	~160.3 μmol/h		~72.6 μmol/h					[74]
Er₂Ti₂O₇		NiO_x		water		400 W mercury lamp	~419.2 μmol/h		~184.9 μmol/h					[74]
Eu₂Ti₂O₇		NiO_x		water		400 W mercury lamp	~17.8 μmol/h		~6.8 μmol/h					[74]
GaN:Mg		RuO₂		water		450 W mercury lamp	~670 μmol/h		~280 μmol/h			21 h (~99%)		[75]
GaN:ZnO		Rh/Cr₂O₃/IrO₂		water (H₂SO₄, pH 4)		300 W Xe lamp (λ > 420 nm)	14 μmol/h		7.1 μmol/h		STH: 0.0125% (1 Sun)	5 h		[76]
GaN:ZnO		RuO₂		water (H₂SO₄, pH 3)		450 W mercury lamp (visible)	~58 μmol/h		~30 μmol/h		AQY: 0.14% (300-480 nm)	15 h (~98%)		[16]
GaN:ZnO		Rh/Cr₂O₃/ Mn₃O₄		water		300 W Xe lamp (λ > 420 nm)	~11.2 μmol/h		~4.9 μmol/h			12 h		[77]
GaN:ZnO		Rh/Cr₂O₃ (ads.)		water		450 W mercury lamp (λ > 400 nm)	426 μmol/h		213 μmol/h			8 h (~99%)		[78]
(Ga_1‒_xZn_x)(N_1‒_xO_x)		Rh-Cr		water (H₂SO₄, pH 4.5)		450 W mercury lamp	~320 μmol/h		~150 μmol/h		AQY: 2.5% (430 nm)	35 h (~97%)		[17]
(Ga_1‒_xZn_x)(N_1‒_xO_x)		RuO₂		water (H₂SO₄, pH 3)		450 W mercury lamp	58 μmol/h		29 μmol/h		AQY: 0.23% (420 nm)			[16]
(Ga_1‒_xZn_x)(N_1‒_xO_x)		Rh/Cr₂O₃		water		450 W mercury lamp (λ > 400 nm)	~175.1 μmol/h		~139 μmol/h			4 h		[79]
(Ga_1‒_xZn_x)(N_1‒_xO_x)		Rh_2‒_yCr_yO₃/SiO₂		water		300 W Xe lamp (λ > 300 nm)	~130.7 μmol/h		~57.7 μmol/h			7 h		[80]
Gd₂Ti₂O₇		NiO_x		water		400 W mercury lamp	~446.6 μmol/h		~228.8 μmol/h					[74]
β-Ge₃N₄		RuO₂		water (H₂SO₄, pH 0)		450 W mercury lamp	467 μmol/h		~233 μmol/h			25 h		[81]
β-Ge₃N₄ (NH₃)		RuO₂		water		450 W mercury lamp	1100 μmol/h		550 μmol/h		AQY: 7.0% (300 nm)	5 h		[82]
Ho₂Ti₂O₇		NiO_x		water		400 W mercury lamp	~564.4 μmol/h		~253.4 μmol/h					[74]
K₂La₂Ti₃O₁₀		Ni/NiO		water (0.1 mol/L KOH)		450 W mercury lamp	444 μmol/h		221 μmol/h			10 h (~99%)		[57]
K₂La₂Ti₃O₁₀		Cr/Ni		water (0.1 mol/L KOH)		450 W mercury lamp	885 μmol/h		442 μmol/h			124 h (~40%)		[83]
K₄Nb₆O₁₇		Ni/NiO		water		450 W mercury lamp	63 μmol/h		31 μmol/h		AQY: 3.5% (330 nm)	50 h (~86%)		[55]
K₄Nb₆O₁₇		NiO		water (pH 9.7)		450 W mercury lamp	124 μmol/h		62 μmol/h		AQY: 5.2% (330 nm)	5 h		[84]
K₂Rb₂Nb₆O₁₇		NiO		water (pH 9.7)		450 W mercury lamp	78 μmol/h		39 μmol/h		AQY: 3.3% (330 nm)	5 h		[84]
LaMg_1/3Ta_2/3O₂N		TiOXH/SiOXH/ RhCrO_y		water		300 W Xe lamp (λ > 300 nm)	~3.6 μmol/h		~1.8 μmol/h		AQY: 0.3% (440 nm)	22 h (~98%)		[85]
LaMg_1/3Ta_2/3O₂N		TiO₂/RhCrO_y		water		300 W Xe lamp (λ > 300 nm)	~1.9 μmol/h		~0.9 μmol/h			5 h		[86]
LaMg_1/3Ta_2/3O₂N		RhCrO_y/SiO₂/ TiO₂		water		300 W Xe lamp (λ > 300 nm)	22 μmol/h		11 μmol/h		AQY: 0.18% (430 nm)	27 h (~99%)		[87]
Lu₂Ti₂O₇		NiO_x		water		400 W mercury lamp	~58.9 μmol/h		~21.9 μmol/h					[74]
Rb₂La₂Ti₃O₁₀		Ni/NiO		water (0.1 mol/L RbOH)		450 W mercury lamp	869 μmol/h		430 μmol/h			30 h (~87%)		[49]
Rb_1.5La₂Ti_2.5Nb_0.5O₁₀		Ni/NiO		water (0.1 mol/L RbOH)		450 W mercury lamp	725 μmol/h		358 μmol/h					[49]
RbLa₂Ti₂NbO₁₀		Ni/NiO		water (0.1 mol/L RbOH)		450 W mercury lamp	79 μmol/h		30 μmol/h					[49]
Rb₄Nb₆O₁₇	NiO		water (pH 9.7)		450 W mercury lamp		228 μmol/h	110 μmol/h		AQY: 10.0% (330 nm)		30 h (~91%)	[84]
SrTaO₂N	CrO_y/Ru/IrO₂		water (NaOH, pH 8)		300 W Xe lamp (λ > 420 nm)		9.1 μmol/h	3.0 μmol/h		AQY: 0.34% (420 nm) STH: ~0.0055% (1 Sun)		18 h (~65%)	[88]
SrTiO₃	NiO_x		water vapor		450 W mercury lamp		4.4 μL/h	2.2 μL/h					[24]
SrTiO₃	Ni/NiO		water		450 W mercury lamp		24.4 μmol/h	10.6 μmol/h				60 h (~95%)	[27]
SrTiO₃	NiO_x		water (5 mol/L OH^-)		450 W mercury lamp		24 μmol/h	~12 μmol/h					[25]
SrTiO₃	Rh₂O₃/Cr₂O₃		water		450 W mercury lamp		~400 μmol/h	~200 μmol/h				5 h	[38]
SrTiO₃:Al	Rh_2‒_yCr_yO₃		water		300 W Xe lamp (λ > 300 nm)		550 μmol/h	280 μmol/h		AQY: 30% (360 nm)		5 h	[41]
SrTiO₃:Al	MoO_x/RhCrO_y		water		300 W Xe lamp (300-500 nm)		~1.8 mmol/h	~0.9 mmol/h		AQY: 60% (365 nm)		16 h (~91%)	[42]
SrTiO₃:Al	Rh/Cr₂O₃/ CoOOH		water		300 W Xe lamp (full arc)		3.54 mmol/h	1.78 mmol/h		EQE: 95.7% (350 nm) STH: 0.65% (1 Sun)		12.5 (~94%)	[46]
SrTiO₃:Al	RhCrO_y/CoO_y		water vapor		20 mW UV LED (365 nm)		~0.9 μmol/h	~0.4 μmol/h		AQY: 0.86% (365 nm)		6 h	[89]
SrTiO₃:Al [100 m² panel]	Rh_2‒_yCr_yO₃/ CoO_x		water		Natural sunlight		oxyhydrogen: 568 mL/min			STH: 0.76%		1600 h (~79%)	[15]
SrTiO₃:Ga	Rh₂O₃/Cr₂O₃		water		450 W mercury lamp		~4.3 mmol/h	~2.2 mmol/h				2 h	[38]
SrTiO₃:Ga, La	Rh₂O₃/Cr₂O₃		water		450 W mercury lamp		~1200 μmol/h	~600 μmol/h				2 h	[38]
SrTiO₃:La	Rh₂O₃/Cr₂O₃		water		450 W mercury lamp		~100 μmol/h	~50 μmol/h				5 h	[38]
SrTiO₃:Na	Rh₂O₃/Cr₂O₃		water		450 W mercury lamp		~10.1 mmol/h	~5.2 mmol/h				1.5 h	[38]
SrTiO₃:Na, Ta	Rh₂O₃/Cr₂O₃		water		450 W mercury lamp		~400 μmol/h	~200 μmol/h				5 h	[38]
SrTiO₃:Ta	Rh₂O₃/Cr₂O₃		water		450 W mercury lamp		~200 μmol/h	~100 μmol/h				5 h	[38]
Ta₃N₅	Rh/Cr₂O₃		water		300 W Xe lamp (λ > 420 nm)		~10.9 μmol/h	~4.8 μmol/h		AQY: 2.2% (320 nm) STH: 0.014% (1 Sun)		15 h (~90%)	[90]
TaON:Zr	Ru/Cr₂O₃/IrO₂		water (NaOH, pH 8.0)		300 W Xe lamp (λ > 380 nm)		~13.7 μmol/h	~ 6.3 μmol/h		AQY: 0.81% (365 nm) STH: 0.009% (0.8 Sun)		24 h (82%)	[91]
Tm₂Ti₂O₇	NiO_x		water		400 W mercury lamp		~237.0 μmol/h	~106.9 μmol/h					[74]
Yb₂Ti₂O₇	NiO_x		water		400 W mercury lamp		~198.6 μmol/h	~94.5 μmol/h					[74]
Y₂Ti₂O₅S₂	IrO₂/Rh/Cr₂O₃		water (La₂O₃, pH 8.5)		300 W Xe lamp (λ > 420 nm)		~6.4 μmol/h	~3.2 μmol/h		AQY: 0.36% (420 nm) STH: 0.007% (1 Sun)		20 h (~81%)	[92]
ZrO₂:TaON	IrO₂/Cr₂O₃/ RuO_x		water		450 W mercury lamp (visible)		~3.0 μmol/h	~1.4 μmol/h		AQY: ~0.1% (420 nm)		16 h	[93]
(Zn₁₊_xGe)(N₂O_x)	Rh_2‒_yCr_yO₃		water		300 W Xe lamp (λ > 420 nm)		11.1 μmol/h	5.4 μmol/h		AQY: 0.20% (420 nm)		50 h (~87%)	[94]
(Zn_1.44Ge)(N₂O_0.44)	RuO₂		Water		420 W mercury lamp (visible)		14.2 μmol/h	7.4 μmol/h				10 h (~99%)	[95]
(Zn_1.44Ge)(N₂O_0.44)	Rh_yCr_2‒_yO₃		water		450 W mercury lamp (λ > 400 nm)		~520.6 μmol/h	~262.7 μmol/h		AQY: 2.0% (430 nm)			[96]

Photocatalytic system					Surface modification		Reaction medium	Light source		Gas evolution rate			Efficiency ^b		Duration (stability)^c			Ref.
HEP	OEP		Mediator		Surface modification		Reaction medium	Light source		H₂	O₂		Efficiency ^b		Duration (stability)^c			Ref.
BaTaO₂N	WO₃		IO₃^-/I^-		Pt		water (5 mmol/L NaI)	300 W Xe lamp (> 420 nm)		~6.6 μmol/h	~3.1 μmol/h		AQY: 0.1% (430 nm)		50 h (~54%)			[120]
BaTaO₂N- RbCl	WO₃		IO₃^-/I^-		Pt/PtO_x		water (1 mmol/L NaI)	300 W Xe lamp (> 420 nm)		~242 μmol/h	~114 μmol/h		AQY: 4.0% (420 nm) STH: 0.24%		10 h			[123]
CaTaO₂N	WO₃		IO₃^-/I^-		Pt		water (5 mmol/L NaI)	300 W Xe lamp (> 420 nm)		~4.3 μmol/h	~2.0 μmol/h				16 h (~97%)			[119]
LaMg_1/3Ta_2/3O₂N	BiVO₄:Mo		Au		RhCrO_x/ TiO₂		water	300 W Xe lamp (> 420 nm)		~1.1 μmol/h	~0.6 μmol/h		AQY: 0.07% (418 nm) STH: 0.001% (1 Sun)		8 h			[212]
La₅Ti₂AgS₅O₇	WO₃: H⁺,Cs⁺		IO₃^-/I^-		Pt/NiS/ PtO_x		water (2.5 mmol/L NaI)	300 W Xe lamp (> 420 nm)		11.1 μmol/h	5.4 μmol/h		AQY: 0.12% (420 nm)		11 h (~61%)			[161]
La₅Ti₂AgS₅O₇	WO₃: H⁺,Cs⁺		IO₃^-/I^-		Pt/PtO_x		water (2.5 mmol/L NaI)	300 W Xe lamp (> 420 nm)		5.6 μmol/h	2.6 μmol/h							[161]
La₅Ti₂AgS₅O₇	WO₃: H⁺,Cs⁺		IO₃^-/I^-		NiS/PtO_x		water (2.5 mmol/L NaI)	300 W Xe lamp (> 420 nm)		2.3 μmol/h	1.1 μmol/h							[161]
La₅Ti₂Cu_0.9Ag_0.1S₅O₇	WO₃: H⁺,Cs⁺		IO₃^-/I^-		Pt/NiS/ PtO_x		water (2.5 mmol/L NaI)	300 W Xe lamp (> 420 nm)		3.7 μmol/h	1.8 μmol/h							[161]
La₅Ti₂Cu_0.9Ag_0.1S₅O₇:Ga	WO₃: H⁺,Cs⁺		IO₃^-/I^-		Pt/NiS/ PtO_x		water (2.5 mmol/L NaI)	300 W Xe lamp (> 420 nm)		1.9 μmol/h	0.9 μmol/h							[161]
La₅Ti₂Cu_0.9Ag_0.1S₅O₇:Ga	WO₃: H⁺,Cs⁺		IO₃^-/I^-		Rh/Cr₂O₃/ PtO_x		water (15 mmol/L NaI, H₂SO₄, pH 4)	300 W Xe lamp (> 420 nm)		~30.9 μmol/h	~14.2 μmol/h		AQY: 2.4% (420 nm)		9 h (~80%)			[162]
La₅Ti₂Cu_0.9Ag_0.1S₅O₇:Ga	LaTiO₂N		Au		Rh/CoO_x		water (NaOH, pH 11.0)	300 W Xe lamp (> 420 nm)		~0.51 μmol/h	~0.18 μmol/h		AQY: 0.04% (420 nm)		22 h (~55%)			[117]
La₅Ti₂Cu_0.9Ag_0.1S₅O₇:Ga	BiVO₄		Au		Rh/Cr₂O₃		water	300 W Xe lamp (> 420 nm)		22.0 μmol/h	11.0 μmol/h		AQY: 3.2% (420 nm) STH: 0.11% (1 Sun)		12 h (~99%)			[163]
La₅Ti₂Cu_0.9Ag_0.1S₅O₇:Ga	BiVO₄:Mo		Au		Rh/Cr₂O₃/ CoO_x		water	300 W Xe lamp (> 420 nm)		~75.6 μmol/h	~35.0 μmol/h		AQY: 11.8% (420 nm) STH: 0.4% (1 Sun)		8 h			[165]
La₅Ti₂Cu_0.9Ag_0.1S₅O₇:Mg,Al	BiVO₄:Mo		Au		CoO_x/Cr₂O₃ /Rh		water	300 W Xe lamp (> 420 nm)		~97.5 μmol/h	~49.5 μmol/h		AQY: 16.3% (420 nm) STH: 0.67% (1 Sun)		20 h (~94%)			[164]
La₅Ti₂Cu_0.9Ag_0.1S₅O₇:Mg,Al	BiVO₄:Mo		Au		CoO_x/Cr₂O₃/ Rh/SiO₂		water	300 W Xe lamp (> 420 nm)		~52.3 μmol/h	~23.7 μmol/h		AQY: 9.7% (420 nm) STH: 0.41% (1 Sun)		4 h			[164]
La₅Ti₂CuS₅O₇	WO₃: H⁺, Cs⁺		IO₃^-/I^-		Pt/PtO_x		water (2.5 mmol/L NaI, pH 6.5)	300 W Xe lamp (> 420 nm)		1.1 μmol/h	0.3 μmol/h				60 h (~70%)			[154]
La₅Ti₂CuS₅O₇	WO₃: H⁺,Cs⁺		IO₃^-/I^-		Pt/NiS/PtO_x		water (2.5 mmol/L NaI)	300 W Xe lamp (> 420 nm)		7.5 μmol/h	3.7 μmol/h				4 h			[161]
La₅Ti₂CuS₅O₇	BiVO₄		Au		Rh/Cr₂O₃		Water	300 W Xe lamp (> 420 nm)		4.7 μmol/h	2.3 μmol/h				6 h			[163]
La₆Ti₂S₈O₅	WO₃: H⁺,Cs⁺		IO₃^-/I^-		Rh/PtO_x		Water (2.5 mmol/L NaI, pH 6.5)	300 W Xe lamp (> 420 nm)		0.3 μmol/h	0.1 μmol/h				10 h			[154]
MgTa₂O₆_-xN_y:TaON	BiVO₄		Fe³⁺/Fe²⁺		Rh/Cr		water (25 mmol/L Na₃PO₄, pH 6.0, 10 mmol/L K₄[Fe(CN)₆])	300 W Xe lamp (> 420 nm)		~160 μmol/h	~80 μmol/h		AQY: ~12.3% (420 nm)		4 h			[108]
MgTa₂O₆_-xN_y:TaON	WO₃		IO₃^-/I^-		Pt/PtO_x		water (1 mmol/L NaI)	300 W Xe lamp (> 420 nm)		108.3 μmol/h	55.3 μmol/h		AQY: 6.8% (420 nm)					[106]
Sm₂Ti₂S₂O₅	TiO₂		IO₃^-/I^-		Pt		water (50 mmol/L NaI, pH 12)	420 W mercury lamp		9.0 μmol/h	3.2 μmol/h				14 h (~38%)			[151]
Sm₂Ti₂S₂O₅	BiVO₄				Co/Cr/Pt/Ir		water	300 W Xe lamp (> 420 nm)		1.6 μmol/h	0.8 μmol/h							[211]
Sm₂Ti₂S₂O₅	BiVO₄		Fe³⁺/Fe²⁺		Co/Cr/Pt/Ir		water (2 mmol/L FeCl₃, pH 2.3)	300 W Xe lamp (> 420 nm)		114.7 μmol/h	54.6 μmol/h							[211]
Sm₂Ti₂S₂O₅	BiVO₄		reduced graphene oxide		Co/Cr/Pt/Ir		water	300 W Xe lamp (> 420 nm)		169 μmol/h	74 μmol/h							[211]
Sm₂Ti₂S₂O₅	BiVO₄		Carbon nanotubes		Co/Cr/Pt/Ir		water	300 W Xe lamp (> 420 nm)		175 μmol/h	75 μmol/h		AQY: 5.1% (420 nm) STH: 0.16% (1 Sun)		84 h (~82%)			[211]
Sm₂Ti₂S₂O₅	BiVO₄		rGO		Cr₂O₃/Pt/ IrO₂/CoO_x		water	300 W Xe lamp (> 420 nm)		240 μmol/h	115 μmol/h		AQY: 7.0% (420 nm) STH: 0.22% (1 Sun)		108 h (~81%)			[152]
Sm₂Ti₂S₂O₅		WO₃: H⁺,Cs⁺		IO₃^-/I^-		Pt/IrO₂/ PtO_x	water (2.5 mmol/L NaI, pH 6.5)	300 W Xe lamp (> 420 nm)	4.1 μmol/h			1.6 μmol/h				10 h	[154]
SrTaO₂N		BiVO₄		Fe³⁺/Fe²⁺		Pt/Cr₂O₃/ Ir-FeCoO_x	water (25 mmol/L Na₃PO₄, pH 6.0, 5 mmol/L K₄[Fe(CN)₆])	300 W Xe lamp (AM 1.5G)	~17.8 μmol/h			~7.7 μmol/h		AQY: 4.0% (420 nm) STH: 0.15% (0.87 Sun)		33 h (~92%)	[124]
SrTiO₃:Rh		GaN:ZnO		Fe³⁺/Fe²⁺		Ru/Au/IrO₂	water (2 mmol/L FeCl₃, H₂SO₄, pH 2.75)	300 W Xe lamp (> 420 nm)	38 μmol/h			17.8 μmol/h		STH: 0.037% (1 Sun)		100 h (~92%)	[76]
SrTiO₃:La,Rh		BiVO₄:Mo		Au		Ru/RuO_x	water	300 W Xe lamp (> 420 nm)	~94.1 μmol/h			~46.2 μmol/h		AQY: 30% (419 nm) STH: 1.1% (1 Sun)		13 h (~99%)	[13]
SrTiO₃:La,Rh		BiVO₄:Mo		Au		Ru/RuO_x	water	300 W Xe lamp (> 420 nm)	4.0 μmol/ (h∙cm²)			2.0 μmol/ (h∙cm²)		AQY: 5.9% (418 nm) STH: 0.2% (0.9 Sun)		8 h	[213]
SrTiO₃:La,Rh		BiVO₄:Mo		C		Ru/RuO_x	water	300 W Xe lamp (> 420 nm)	8.6 μmol/ (h∙cm²)			4.4 μmol/ (h∙cm²)		AQY: 26% (419 nm) STH: 1.0% (1 Sun)		17 h (~99%)	[214]
SrTiO₃:La,Rh		BiVO₄:Mo		C		Ru/RuO_x	water (pH 3.5)	300 W Xe lamp (> 420 nm)	11 μmol/ (h∙cm²)			5.5 μmol/ (h∙cm²)					[214]
SrTiO₃:Rh		BiVO₄:Mo		ITO		Ru/RuO_x	water	300 W Xe lamp (> 420 nm)	6.5 μmol/ (h∙cm²)			3.2 μmol/ (h∙cm²)		AQY: 10.2% (420 nm) STH: 0.4% (1 Sun)		48 h (~84%)	[215]
TaON		BiVO₄		Fe³⁺/Fe²⁺		Rh_yCr₂_-yO₃/ Ir/IrO₂	water (25 mmol/L Na₃PO₄, pH 6.0, 10 mmol/L K₄[Fe(CN)₆])	300 W Xe lamp (> 420 nm)	~200 μmol/h			~100 μmol/h		AQY: 16.9% (420 nm) STH: 0.8% (1 Sun)		4.5 h (~98%)	[107]
TaON		WO₃		IO₃^-/I^-		Pt/PtO_x	water (1 mmol/L NaI)	300 W Xe lamp (> 420 nm)	15.6 μmol/h			7.5 μmol/h					[106]
TaON		WO₃		IO₃^-/I^-		Pt	water (5 mmol/L NaI)	300 W Xe lamp (> 400 nm)	24 μmol/h			12 μmol/h		AQY: 0.4% (420 nm)		100 h	[206]
TaON		WO₃		IO₃^-/I^-		Pt/PtO_x	water (5 mmol/L NaI, pH 6.5)	300 W Xe lamp (> 400 nm)	~18.7 μmol/h			~8.5 μmol/h		AQY: 0.5% (420 nm)		19 h (~99%)	[207]
TaON		TaON		IO₃^-/I^-		Pt/RuO₂	water (1 mmol/L NaI)	300 W Xe lamp (> 420 nm)	~7.2 μmol/h			~2.8 μmol/h		AQY: ~0.1% (420 nm)		10 h (~43 %)	[208]
TiO₂ (anatase)		TiO₂ (rutile)		IO₃^-/I^-		Pt	water (0.1 mol/L NaI, pH 11)	400 mercury lamp	~141.8 μmol/h			~70.9 μmol/h				20 h (~98%)	[203]
(ZnSe)_0.5(CuGa_2.5Se_4.25)_0.5		BiVO₄:Mo		Au		Pt/CdS/TiO₂	Water	300 W Xe lamp (> 420 nm)	12 μmol/h			6 μmol/h		AQY: 1.5% (420 nm)		5 h	[216]
m-ZrO₂:TaON		WO₃		IO₃^-/I^-		Pt	water (1 mmol/L IO₃^-/I^-)	300 W Xe lamp (> 420 nm)	~4.2 μmol/h			~1.36 μmol/h				40 h (~ 99%)	[103]
ZrO₂:TaON		BiVO₄		Fe³⁺/Fe²⁺		Rh/Cr	water (25 mmol/L Na₃PO₄, pH 6.0, 10 mmol/L K₄[Fe(CN)₆])	300 W Xe lamp (> 420 nm)	~160 μmol/h			~80 μmol/h		AQY: 12.3% (420 nm) STH: 0.6% (1 Sun)		50 h (~98%)	[108]
ZrO₂:TaON		WO₃		IO₃^-/I^-		Pt	water (1.0 mmol/L NaI)	300 W Xe lamp (> 420 nm)	32.6 μmol/h			15.6 μmol/h		AQY: 6.3% (420 nm)		10 h (~90%)	[171]

Novel materials and techniques for photocatalytic water splitting developed by Professor Kazunari Domen

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Strategy	Description
Doping	introducing bandgap narrowing through interactions of cation states with valence or conduction bands, or creating intrabandgap levels; suppressing the formation of “killer defects” (enhancing η_absorption and η_separation)
(Oxy)nitride and oxysulfide	modifying the VB by incorporating N 2p or S 2p anions, leading to a narrowed bandgap (enhancing η_absorption)
Solid solution	adjusting bandgaps and energy levels by varying the ratios of wide- and narrow-bandgap semiconductors (enhancing η_absorption)
Z-scheme system	utilizing a two-step photoexcitation process with an HEP and an OEP, both with narrow bandgaps (enhancing η_absorption and η_separation)
Flux treatment	tailoring crystallinity and grain boundary structure to limit defect formation (enhancing η_separation)
Combination of different cocatalyst deposition methods	enhancing cocatalyst dispersion and creating additional active sites (enhancing η_separation and η_reaction)
Co-deposition of HEC and OEC	promoting charge separation by providing both reductive and oxidative active sites; spatially separating HEC and OEC through facet engineering (enhancing η_separation and η_reaction)
Two-component cocatalysts	improving charge transport from the light absorber to the cocatalyst (enhancing η_separation and η_reaction)
Surface modification for HEC and photocatalyst	effectively suppressing back reactions on the surface of HEC and light absorbers (enhancing η_reaction)
Particle transfer method	effectively facilitating charge separation and transfer between HEP and OEP in a Z-scheme configuration, or between the photocatalyst and the substrate in a photoelectrode (enhancing η_separation)

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