Recent advances in the development of bismuth-based materials for the photocatalytic reduction of hexavalent chromium in water

doi:10.1016/S1872-2067(23)64553-X

Chinese Journal of Catalysis ›› 2023, Vol. 55: 20-43.DOI: 10.1016/S1872-2067(23)64553-X

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Recent advances in the development of bismuth-based materials for the photocatalytic reduction of hexavalent chromium in water

Yang Sun^a, Jan E. Szulejko^a, Ki-Hyun Kim^a^,^*(), Vanish Kumar^b^,^*(), Xiaowei Li^c^,^*()

^aDepartment of Civil and Environmental Engineering, Hanyang University, Seoul 04673, Korea
^bNational Agri-Food Biotechnology Institute (NABI), S.A.S. Nagar, Punjab 140306, India
^cSchool of Environmental and Chemical Engineering, Organic Compound Pollution Control Engineering, Ministry of Education, Shanghai University, Shanghai 200444, China

Received:2023-08-13 Accepted:2023-10-11 Online:2023-12-18 Published:2023-12-07
Contact: *E-mail: kkim61@hanyang.ac.kr (K.-H. Kim), vanish.saini01@gmail.com (V. Kumar), lixiaowei419@shu.edu.cn (X. Li).
About author:Prof. Ki-Hyun Kim was at Florida State University for an M.S. (1984‒1986) and at University of South Florida for a Ph.D. (1988‒1992). He was a Research Associate at Oak Ridge National Laboratory, USA (1992 to 1994). He moved to Sang Ji University, Korea in 1995 and then joined Sejong University in 1999. In 2014, he moved to the Department of Civil & Environmental Engineering at Hanyang University. His research areas cover the various aspects of research to incorporate “Air Quality & Environmental Engineering” into “Material Engineering” with emphasis on Metal-Organic Frameworks (MOFs). He was awarded as one of the top 10 National Star Faculties in Korea in 2006 and became an academician (Korean Academy of Science and Technology) in 2018. He has been recognized as ‘Highly Cited Researcher (HCR)’ in dual fields of ‘Environment & Ecology’ and ‘Engineering’ from Clarivate Analytics. He is serving as associate editor of ‘Environmental Research’, Sensors’, and ‘Critical Reviews in Environmental Science & Technology’. He has published more than 980 articles, many of which are in leading scientific journals including Chemical Society Reviews, Progress in Material Science, Progress in Energy and Combustion Science, Chem, Nano Energy, Coordination Chemistry Reviews, Applied Catalysis B, and Chemical Engineering Journal.
Dr. Vanish Kumar is presently working as Scientist at National Agri-Food Biotechnology Institute, Mohali, India. He has an M. Tech degree in nanoscience and nanotechnology. He completed his PhD (Engineering) from Academy of Scientific and Innovative Research (AcSIR) CSIR-CSIO, Chandigarh, India. His current areas of research include development of advanced nanostructures for sensing/removal of contaminants/pollutants and analytical applications of nanomaterials. He has published more than 90 research papers in reputed international journals.
Xiaowei Li (School of Environmental and Chemical Engineering, Shanghai University) received his Ph.D degree in 2012 from Tongji University. From 2013 to 2015, he did postdoctoral research at Tongji University. Since 2016, he joined the faculty of Department of Environmental Science and Engineering, Shanghai University. His research interests currently focus on environmental risk and photocatalysis degradation of emerging pollutants (such as microplastics in wastewater and sewage sludge) and harmless treatment/resource utilization of organic waste (such as sewage sludge, food waste, and human excreta). He has coauthored more than 80 peer-reviewed journal articles.

Abstract

Abstract:

abstract: Photocatalytic reduction (PCR) is an emerging option to treat hexavalent chromium (Cr(VI)) in aquatic systems. The lamellar bismuth (Bi)-based materials are recognized as a potential platform for PCR against Cr(VI) with enhanced light harvesting ability and tunable bandgap energy. The PCR mechanism of Bi-based materials against Cr(VI) has been explored in relation to the modification strategies (e.g., heterojunction, defect engineering, and doping) and to the process variables (e.g., solution pH and the type/quantity of additives). Performance evaluation of diverse Bi-based materials has also been made using a figure of merit (FoM) as the key metric for industrially relevant conditions. Accordingly, shuriken-shaped BiVO₄ with average particle sizes of 5‒10 nm was recognized as the best performer with the highest FoM value (3.45 × 10^-5 mol g^-1 Wh^-1). To scale up the utility of Bi-based materials against Cr(VI), further efforts should be directed toward drastic reduction of treatment costs for real-world applications, especially in terms of catalyst fabrication and energy consumption (due to poor quantum yield).

Key words: Photocatalyst, Chromium, Semiconductor, Bismuth, Figure of merit

Yang Sun, Jan E. Szulejko, Ki-Hyun Kim, Vanish Kumar, Xiaowei Li. Recent advances in the development of bismuth-based materials for the photocatalytic reduction of hexavalent chromium in water[J]. Chinese Journal of Catalysis, 2023, 55: 20-43.

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Order	Year	Cr(VI) reduction/removal method	Material			Performance evaluation	Advantage	Disadvantage		Ref.
1	2010	adsorption	lignocellulosic materials			Pith (Q = 262.89 mg g^‒1)	simply operation Low cost	rapid saturation		[138]
2	2012	electrocoagulation	Iron/Aluminum electrodes			—	simplicity of operation	high energy consumption loss of electrodes		[139]
		photocatalytic reduction	organic matter			—	cost-effective environmental-friendly	unwanted byproducts
			Fe(III) photocatalysts + organic acids
			TiO₂ photocatalysts + organic acid
		Cr(VI) reduction bacteria	aerobic Cr(VI) reducing bacteria			—	economical operation	long period for Cr(VI) treatment
			anaerobic Cr(VI) reducing bacteria
			fungi
3	2016	electrochemical method	carbon-based electrodes gold electrodes conducting polymers			—	high energy efficiency and rapid treatment	pH dependence anode passivation and sludge deposition on the electrodes		[140]
4	2016	photocatalytic Cr(VI) reduction	MOFs semiconductor/MOFs hybrid photocatalyst conductor/MOFs hybrid photocatalyst			—	in situ production of reactive radicals less consumption of chemicals flexible modulation of MOFs	expensive cost for MOFs preparation potential MOFs structure collapse		[141]
5	2018	biological methods	bacteria/fungi/algae/plants			—	eco-friendly and cost-effective	preparation of favorable environment; slow process		[14]
6	2019	catalytic methods	catalysts + carboxylic acids (Cas)			—	fast kinetic; rapid operation ubiquitous presence of Cas in natural environments and effluents	possible generation of uncertain by-products hard to be employed		[142]
7	2019	adsorption	activated carbon, Zero valent iron			—	cheap production	low affinity elimination of adsorbents		[16]
		voagulation	FeCl₃, FeSO₄, Al₂(SO₄)₃			—	high performance	low efficiency additional consumption secondary pollutants
		electrochemical method	—			—	cost-effective rapid treatment	high energy consumption
		ion exchange	—			—	simple process and technology easy to be used with other techniques	highly dependent with pH low binding affinity due to the presence of free acids
		membrane separation	polyamide membranes			—	small required space high quality treated effluent low solid waste generation	generation of residual sludge amount, expensive energy use
		biological methods	—			—	eco-friendly cheap	biological sludge generation microorganisms management and maintenance
		fenton reaction	Fe + H₂O₂			—	fast reaction	extra chemicals
		photocatalysis	—			—	green technology	uncertain byproducts
8	2019	bioremediation technology		biochar	chattim tree saw dust (Q = 333.33 mg g^‒1)		high performance		tedious post treatments expensiveness of regeneration and material loss	[33]
				microorganisms	—		low cost small risk of secondary pollution		long term
				plants	—		low cost small risk of secondary pollution		long term
9	2020	photocatalytic approach		photocatalysts	—		high efficiency low energy consumption		laboratory scale low throughput	[143]
10	2021	bacterial reduction		bacteria	—		cost-effective		pH control and environmental maintenance	[144]
11	2021	adsorption/ photocatalytic reduction		graphene-based materials	—		large surface area		material regeneration	[145]
12	2021	photocatalytic technology		graphitic carbon nitride (g-C₃N₄)	—		solar energy utilization low cost		low efficiency	[65]
13	2021	adsorption		carbon-based adsorbents	bermuda grass (Q = 403.2 mg g^‒1)		simple operation High pH range		rapid saturation adsorbents collection and regeneration	[15]
		membrane technology		filtration/osmosis	—		small space easy operation		high maintenance fee
		photocatalysis		TiO₂	—		rapid reduction		high electron/hole recombination rate
		electrochemical treatment		—	—		high energy efficiency		corrosion of electrode
		microbial treatment		—	—		simple operation economical operation		long period environment maintenance
14	2021	adsorption/ photocatalytic reduction		MOFs	—		flexible designing of MOFs		high cost	[146]
15	2021	adsorption/ photocatalytic reduction		polysaccharide-based materials	—		biodegradability and biocompatibility		material preparation	[147]
16	2021	electrochemical reduction method		—	—		versatility		anode passivation	[4]
17	2022	photocatalytic method		photocatalysts	—		no sludge production		pH dependence	[148]
18	2022	photo-reduction method		MOF-based photocatalyst	—		unique versatilities facile structural modulation		expensive	[149]
19	2022	microbial immobilization technology		—	—		eco-friendly		complexity of the operation	[150]
20	2022	adsorption		surface-modified silicas	silica modified with 1-methyl-3-(triethoxysilypropyl) imidazolium chloride (Q = 428 mg g^‒1)		high performance		regeneration	[34]
21	2022	photocatalytic method		MOFs-based photocatalysts	—		wide range of MOFs		laboratory scale	[132]
22	2022	photocatalytic method		semiconductor heterojunctions	—		large amount of candidates		energy utilization efficiency	[151]
23	2023	photocatalytic reduction		Bi-based photocatalysts	BiVO₄ FoM = 3.45 × 10^‒5 mol g^‒1 Wh^‒1		abundance adjustable optical property high efficiency environment harmless		laboratory scale lack of cost/energy evaluation	this work

Order	Year	Cr(VI) reduction/removal method	Material			Performance evaluation	Advantage	Disadvantage		Ref.
1	2010	adsorption	lignocellulosic materials			Pith (Q = 262.89 mg g^‒1)	simply operation Low cost	rapid saturation		[138]
2	2012	electrocoagulation	Iron/Aluminum electrodes			—	simplicity of operation	high energy consumption loss of electrodes		[139]
		photocatalytic reduction	organic matter			—	cost-effective environmental-friendly	unwanted byproducts
			Fe(III) photocatalysts + organic acids
			TiO₂ photocatalysts + organic acid
		Cr(VI) reduction bacteria	aerobic Cr(VI) reducing bacteria			—	economical operation	long period for Cr(VI) treatment
			anaerobic Cr(VI) reducing bacteria
			fungi
3	2016	electrochemical method	carbon-based electrodes gold electrodes conducting polymers			—	high energy efficiency and rapid treatment	pH dependence anode passivation and sludge deposition on the electrodes		[140]
4	2016	photocatalytic Cr(VI) reduction	MOFs semiconductor/MOFs hybrid photocatalyst conductor/MOFs hybrid photocatalyst			—	in situ production of reactive radicals less consumption of chemicals flexible modulation of MOFs	expensive cost for MOFs preparation potential MOFs structure collapse		[141]
5	2018	biological methods	bacteria/fungi/algae/plants			—	eco-friendly and cost-effective	preparation of favorable environment; slow process		[14]
6	2019	catalytic methods	catalysts + carboxylic acids (Cas)			—	fast kinetic; rapid operation ubiquitous presence of Cas in natural environments and effluents	possible generation of uncertain by-products hard to be employed		[142]
7	2019	adsorption	activated carbon, Zero valent iron			—	cheap production	low affinity elimination of adsorbents		[16]
		voagulation	FeCl₃, FeSO₄, Al₂(SO₄)₃			—	high performance	low efficiency additional consumption secondary pollutants
		electrochemical method	—			—	cost-effective rapid treatment	high energy consumption
		ion exchange	—			—	simple process and technology easy to be used with other techniques	highly dependent with pH low binding affinity due to the presence of free acids
		membrane separation	polyamide membranes			—	small required space high quality treated effluent low solid waste generation	generation of residual sludge amount, expensive energy use
		biological methods	—			—	eco-friendly cheap	biological sludge generation microorganisms management and maintenance
		fenton reaction	Fe + H₂O₂			—	fast reaction	extra chemicals
		photocatalysis	—			—	green technology	uncertain byproducts
8	2019	bioremediation technology		biochar	chattim tree saw dust (Q = 333.33 mg g^‒1)		high performance		tedious post treatments expensiveness of regeneration and material loss	[33]
				microorganisms	—		low cost small risk of secondary pollution		long term
				plants	—		low cost small risk of secondary pollution		long term
9	2020	photocatalytic approach		photocatalysts	—		high efficiency low energy consumption		laboratory scale low throughput	[143]
10	2021	bacterial reduction		bacteria	—		cost-effective		pH control and environmental maintenance	[144]
11	2021	adsorption/ photocatalytic reduction		graphene-based materials	—		large surface area		material regeneration	[145]
12	2021	photocatalytic technology		graphitic carbon nitride (g-C₃N₄)	—		solar energy utilization low cost		low efficiency	[65]
13	2021	adsorption		carbon-based adsorbents	bermuda grass (Q = 403.2 mg g^‒1)		simple operation High pH range		rapid saturation adsorbents collection and regeneration	[15]
		membrane technology		filtration/osmosis	—		small space easy operation		high maintenance fee
		photocatalysis		TiO₂	—		rapid reduction		high electron/hole recombination rate
		electrochemical treatment		—	—		high energy efficiency		corrosion of electrode
		microbial treatment		—	—		simple operation economical operation		long period environment maintenance
14	2021	adsorption/ photocatalytic reduction		MOFs	—		flexible designing of MOFs		high cost	[146]
15	2021	adsorption/ photocatalytic reduction		polysaccharide-based materials	—		biodegradability and biocompatibility		material preparation	[147]
16	2021	electrochemical reduction method		—	—		versatility		anode passivation	[4]
17	2022	photocatalytic method		photocatalysts	—		no sludge production		pH dependence	[148]
18	2022	photo-reduction method		MOF-based photocatalyst	—		unique versatilities facile structural modulation		expensive	[149]
19	2022	microbial immobilization technology		—	—		eco-friendly		complexity of the operation	[150]
20	2022	adsorption		surface-modified silicas	silica modified with 1-methyl-3-(triethoxysilypropyl) imidazolium chloride (Q = 428 mg g^‒1)		high performance		regeneration	[34]
21	2022	photocatalytic method		MOFs-based photocatalysts	—		wide range of MOFs		laboratory scale	[132]
22	2022	photocatalytic method		semiconductor heterojunctions	—		large amount of candidates		energy utilization efficiency	[151]
23	2023	photocatalytic reduction		Bi-based photocatalysts	BiVO₄ FoM = 3.45 × 10^‒5 mol g^‒1 Wh^‒1		abundance adjustable optical property high efficiency environment harmless		laboratory scale lack of cost/energy evaluation	this work

Order	Bi-based material	Example	Crystal structure	surface area (m² g^‒1)	UV/visible light response ability	Bandgap energy (E_g, eV)	Estimated light absorption edge (nm)	Ref.
1	Bismuth sulfide	Bi₂S₃	orthorhombic	31.9	visible light near infrared	1.3	~953	[43]
2	Bismuth oxides	Bi₂O₃	monoclinic tetragonal body-centered cubic	1.91	UV/visible light	2.26‒2.95	~420‒548	[44,46,152]
3	Bismuth oxyhalides	BiOCl	tetragonal	18.06	UV	3.3	~375	[153,154]
4		BiOBr	tetragonal	76.38	UV/visible light	2.64	~469	[155]
5		BiOI	tetragonal	52.76	visible light	1.77	~700	[156]
6	Bi-based multicomponent oxides	Bi₂WO₆	orthorhombic	59.46	UV/visible light	2.91	~426	[157]
7		Bi₂MoO₆	orthorhombic	18.75	UV/visible light	2.62	~473	[158]
8		BiVO₄	monoclinic tetragonal octahedral	115	UV/visible light	2.4	~516	[159]
9		Bi₄Ti₃O₁₂	—	15	UV	3.29	~376	[160]
10	Bi-based metal organic frameworks	IEF-5	monoclinic	30	UV/visible light	2.4	~516	[57]
11		CAU-7	monoclinic	104	UV	3.47	~357	[56,59]
12		CAU-17	—	93.15	UV	3.77	~328	[60]
13		SU-100	monoclinic	395	—	—	—	[58]

Order	Bi-based material	Example	Crystal structure	surface area (m² g^‒1)	UV/visible light response ability	Bandgap energy (E_g, eV)	Estimated light absorption edge (nm)	Ref.
1	Bismuth sulfide	Bi₂S₃	orthorhombic	31.9	visible light near infrared	1.3	~953	[43]
2	Bismuth oxides	Bi₂O₃	monoclinic tetragonal body-centered cubic	1.91	UV/visible light	2.26‒2.95	~420‒548	[44,46,152]
3	Bismuth oxyhalides	BiOCl	tetragonal	18.06	UV	3.3	~375	[153,154]
4		BiOBr	tetragonal	76.38	UV/visible light	2.64	~469	[155]
5		BiOI	tetragonal	52.76	visible light	1.77	~700	[156]
6	Bi-based multicomponent oxides	Bi₂WO₆	orthorhombic	59.46	UV/visible light	2.91	~426	[157]
7		Bi₂MoO₆	orthorhombic	18.75	UV/visible light	2.62	~473	[158]
8		BiVO₄	monoclinic tetragonal octahedral	115	UV/visible light	2.4	~516	[159]
9		Bi₄Ti₃O₁₂	—	15	UV	3.29	~376	[160]
10	Bi-based metal organic frameworks	IEF-5	monoclinic	30	UV/visible light	2.4	~516	[57]
11		CAU-7	monoclinic	104	UV	3.47	~357	[56,59]
12		CAU-17	—	93.15	UV	3.77	~328	[60]
13		SU-100	monoclinic	395	—	—	—	[58]

Order	Photocatalyst	Synthesis method	Modification strategy	Light source	Power of light source (W)	Conc. (g L^-1)	Solution vol. (mL)	Time (min)	Cr(VI) conc. (mg L^-1)	Cr(VI) removal rate (%)	k (min^-1)	FoM (mol g^-1 Wh^-1)	Ref.
I. Heterojunction construction
1	Cd_0.5Zn_0.5S/ Bi₂WO₆	hydrothermal method calcination	S-scheme heterojunction	Xe lamp λ > 420 nm	300	0.2	100	20	20	95.80	0.1593	1.84E-05	[98]
2	Bi₂O₂CO₃/RP	hydrothermal method	S-scheme heterojunction	Xe lamp	300	0.25	20	40	40	99.20	0.22	1.53E-05	[103]
3	BiO_2-_x/BiOCl	solvothermal method	type-I heterojunction	LED	35	0.5	40	120	20	87	0.02994	9.56E-06	[102]
4	Bi_xO_y/CdS	solvothermal method	heterojunction	Xe lamp	350	0.6	50	30	41.6	100	0.1265	7.62E-06	[100]
5	BiVO₄@Bi₂S₃	hydrothermal method	type-II heterojunction	Xe lamp λ > 420 nm	350	0.7	50	40	50	100	0.071	5.89E-06	[161]
6	Bi₂O₃/HRP	hydrothermal method	heterojunction	Xe lamp	300	0.25	20	40	14	100	0.11775	5.38E-06	[162]
7	BiOCl coated UiO-66-NH₂	oil bath precipitation method	heterojunction	Xe lamp λ > 420 nm	300	0.5	40	20	8	100	0.233	3.08E-06	[66]
8	Bi₂S₃/BiOCl @ZnIn₂S₄	oil bath	heterojunction	Xe lamp λ > 420 nm	300	1.0	40	60	50	85	0.0293	2.72E-06	[73]
9	Bi₂S₃@NH₂- MIL-125(Ti)	solvothermal method	heterojunction	Xe lamp λ > 420 nm	300	0.1	N.A.	120	10	77	0.01134	2.47E-06	[97]
10	TCPP/GQDs/ Bi₂MoO₆	solvothermal method	Z-scheme heterojunction	Xe lamp λ > 420 nm	300	0.25	80	60	10	90.70	0.0364	2.33E-06	[27]
11	BiOBr/g-C₃N₄	in situ deposition method	Z-scheme heterojunction	Xe lamp λ > 420 nm	300	0.4	120	50	10	~90	—	1.73E-06	[163]
12	AgI/Bi₂₄O₃₁Cl₁₀	in situ precipitation method	Z-scheme heterojunction	Xe lamp	300	0.3	100	60	10	78.26	0.0236	1.67E-06	[16]
13	BiVO₄/Bi₂S₃	solvothermal method	type-II heterojunction	Xe lamp	300	1.0	300	150	50	100	—	1.28E-06	[20]
14	MIL-125-NH₂@BiOI	solvothermal method	type-II heterojunction	Xe lamp λ > 400 nm	300	1.0	40	120	40	100	—	1.28E-06	[114]
15	Bi₂O₃ QDs/g-C₃N₄	wet impregnation manual grinding	heterojunction	Xe lamp λ > 420 nm	300	0.5	100	60	10	87.90	0.0335	1.13E-06	[164]
16	Bi₂S₃/BiVO₄	hydrothermal method	Z-scheme heterojunction	Xe lamp λ > 420 nm	300	1.0	50	180	50	100	—	1.07E-06	[25]
17	BUC-21/ Bi₂₄O₃₁Br₁₀	hydrothermal method	heterojunction	Xe lamp	500	0.25	200	120	10	99.90	0.06287	7.68E-07	[22]
18	Bi₂MoO₆/CeO₂	solvothermal method	type-II heterojunction	Xe lamp λ > 420 nm	300	0.6	50	90	10	98.40	—	7.01E-07	[165]
19	Bi₂S₃@CdS @rGO	hydrothermal method	S scheme heterojunction	Xe lamp 800 nm > λ > 420 nm	300	0.6	50	150	20	81.51	0.0155	6.97E-07	[39]
20	Bi₁₂O₁₇Cl₂/ MIL-100(Fe)	solvothermal method	type-II heterojunction	Xe lamp	300	0.5	200	120	10	~100	0.00483	6.41E-07	[23]
21	MIL-53(Fe)/ Bi₁₂O₁₇C_l2	solvothermal method	Z-scheme heterojunction	Xe lamp	500	0.5	100	90	10	99.20	0.0284	5.09E-07	[166]
22	ZnO-Ag-BiVO₄	hydrothermal method	Z-scheme heterojunction	tungsten lamp λ > 400 nm	150	0.4	100	70	1.7	97	0.0371	4.53E-07	[28]
23	Bi₃NbO₇/BiOCl	hydrothermal method	Z-scheme heterojunction	Xe lamp λ > 400 nm	300	0.5	50	40	1.7	94	0.0864	3.07E-07	[29]
24	KmoP@CdS @Bi₂S₃	hydrothermal method	Z-scheme heterojunction	Xe lamp 780 nm > λ > 420 nm	300	1.0	30	120	10	95.50	—	3.06E-07	[167]
25	Bi₄Ti₃O₁₂/ Bi₂Ti₂O₇	calcination	type-II heterojunction	Xe lamp λ > 400 nm	300	1.5	100	120	0.7	39	0.0034	6.02E-09	[104]
26	Ag/AgBr/BiVO₄	hydrothermal method	Z-scheme heterojunction	Xe lamp λ > 420 nm	300	N.A.	60	60	10	91.72	0.0405	N.A.	[168]
										average FoM value	3.41E-06
II. Defect engineering
1	BiSI	solvothermal/ hydrothermal method	O doping sulfur vacancy	Xe lamp	300	1.0	50	30	20	~100	0.191	2.56E-06	[101]
2	Bi₄O₅Br₂/Bi₂S₃	hydrothermal method	Z-scheme heterojunction oxygen vacancy	Xe lamp	500	0.4	800	80	20	91.30	0.02363	1.32E-06	[75]
3	Bi_3.25La_0.75Ti₃O_12-_x	hydrothermal method	oxygen vacancy La doping	Xe lamp λ > 420 nm	300	0.4	100	200	20	95.10		9.14E-07	[31]
4	N-SSC/Bi₂WO₆	hydrothermal method	oxygen vacancy	Xe lamp λ > 420 nm	300	1.0	50	120	10	28	0.0031	8.97E-08	[30]
5	Bi_.33(Bi₆S₉) Br/Bi₂S₃	hydrothermal method	Z-scheme heterojunction sulfur defect	Xe lamp λ > 420 nm	300	0.2	50	60	N.A.	94.40	0.0488	N.A.	[66]
III. Element doping
1	Ca-doped BiFeO₃	combustion method	Ca doping	Xe lamp	35	0.4	50	210	17.5	89.92	0.00364	6.18E-06	[126]
2	In-doped Bi₂MoO₆	hydrothermal- calcination process	In doping	Xe lamp λ > 420 nm	300	0.5	40	30	20	98	0.0626	5.03E-06	[123]
3	Sn-doped BiOBr	hydrothermal method	Sn doping	Xe lamp	300	0.4	50	60	15	~90	0.33316	2.16E-06	[124]
4	Cl-doped Bi₂S₃	hydrothermal method	Cl doping	Xe lamp λ > 420 nm	300	0.2	50	100	10	96.60	0.0357	1.86E-06	[38]
5	Bi₂S₃/Ag	hydrothermal method	Ag doping	Xe lamp 700 nm > λ > 400 nm	300	0.5	100	75	10	97.00	0.0455	9.95E-07	[32]
6	I-BiOBr/ Bi₁₂GeO₂₀	water bath method	Z-scheme heterojunction I doping	Xe lamp λ > 420 nm	250	0.5	100	60	10	~60	0.0113	9.23E-07	[125]
7	CrO₄^2- intercalated BiOBr	hydrothermal method	CrO₄^2- doping	Xe lamp λ > 420 nm	500	0.4	50	120	10	100	—	4.81E-07	[169]
8	Na₂WO₄BiBDC	hydrothermal method	WO₄^2-doping	Xe lamp λ > 365 nm	350	1.0	50	180	20	70	0.006	2.56E-07	[170]
										average FoM value	2.23E-06
IV. Others
1	BiVO₄	solvothermal method	—	Xe lamp	35	0.2	50	160	35	95.09	0.01626	3.43E-05	[24]
2	CaBiO₃	calcination	—	1200 nm > λ > 300 nm	150	0.9	100	120	364	94	0.0147	2.44E-05	[171]
3	Bi₂MoO₆/Ti₃C₂ Mxene	hydrothermal method	—	LED λ > 400 nm	50	0.5	20	60	15	100	—	1.15E-05	[26]
4	BiOCl	hydrolytic process	—	mercury lamp	150	0.2	N.A.	120	20	~100	0.1076 ¹	6.41E-06	[125]
5	Bi₄O₅I₂ nanosheets	hydrolysis solvothermal approach	—	Xe lamp λ > 420 nm	300	1.0	50	120	60	90	—	1.73E-06	[172]
6	BiOBr/CCNF	calcination hydrothermal method	—	LED	200	0.5	100	90	10	~70	0.21 mmol g^-1 h^-1	8.97E-07	[91]
7	Bi₂O₂CO₃	hydrothermal method	—	Xe lamp	300	0.5	100	30	3.5	97.90	0.6875	8.79E-07	[93]
8	Bi₂Fe₄O₉	calcination	—	tungsten lamp	200	1.5	100	180	25	97	—	5.18E-07	[94]
9	BC/Bi/Fe₃O₄	calcination approach	—	Xe lamp λ > 400 nm	300	1.0	200	180	20	95	0.0114	4.06E-07	[95]
10	Bi₂MoO₆	hydrothermal method	—	Xe lamp λ > 400 nm	300	0.6	50	120	3.5	~95	0.024	1.78E-07	[173]
11	CoFe₂O₄/BiOCl	solvothermal method	—	Xe lamp	300	1.0	10	120	N.A.	78	—	N.A.	[174]

Recent advances in the development of bismuth-based materials for the photocatalytic reduction of hexavalent chromium in water

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Order	Photocatalyst	Light source	Power of light source (W)	Catalyst conc. (g L^-1)	Solution vol. (mL)	Reaction time (min)	Cr(VI) conc. (mg L^-1)	Cr(VI) removal rate (%)	k (min^-1)	FoM (mol g^-1 Wh^-1)	Ref.
I. Noble metal-modified catalysts
1	Ag@TiO₂	mercury lamp	300	0.01	50	60	20	99.80	0.0525	1.28E-04	[134]
2	MIL-53(Fe)/CQDs/AuNPs	Xe lamp	300	0.5	40	30	20	100.00	0.18197	5.13E-06	[175]
3	Pt-UiO-66-NH₂	Xe lamp	300	1.0	40	80	50	~70	—	1.68E-06	[176]
4	TiO₂@Pt@CeO₂	Xe lamp	300	0.3	100	160	5	99.00	—	3.97E-07	[177]
II. MOF-based catalysts
1	JUL-MOF60	Xe lamp	300	0.4	25	70	160	98.00	—	2.15E-05	[178]
2	MIL-100(Fe)/g-C₃N₄	Xe lamp	300	0.5	200	120	10	97.00	0.037	6.22E-07	[179]
3	Cd_0.5Zn_0.5S@ZIF-8	Xe lamp	300	1.0	40	30	20	100.00	—	2.56E-06	[77]
4	TiO₂/MIL-125	Xe lamp	300	0.3	50	60	5	100.00	0.1059	1.07E-06	[86]
III. Metal sulfide catalysts
1	N-CoS_x	Xe lamp	300	0.2	25	25	10	100.00	0.1662	7.69E-06	[180]
2	SnS₂ with SVs	Xe lamp	500	0.2	50	90	50	99.80	0.123	6.40E-06	[181]
3	CoS_x/CdS	Xe lamp	300	0.2	50	30	10	99.80	0.2202	6.40E-06	[182]
4	CaInS₂-decorated WS₂	metal halogen lamp	400	0.5	50	90	80	98.00	0.034	5.03E-06	[183]
IV. g-C₃N₄-based catalysts
1	MgIn₂S₄/O-doped g-C₃N₄	Xe lamp	300	0.5	50	50	20	99.10	0.07605	3.05E-06	[184]
2	N-TiO₂/O-doped N vacancy g-C₃N₄	Xe lamp	300	0.4	100	120	15	89.50	0.0178	1.08E-06	[83]
3	CoS₂/g-C₃N₄-rGO	Xe lamp	350	0.5	20	150	20	99.80	0.0179	8.77E-07	[185]
4	Br-doped g-C₃N₄	Xe lamp	300	1.0	50	120	20	61.60	0.00495	3.95E-07	[186]
V. Other catalysts
1	Mxene/ZnIn₂S₄	Xe lamp	300	0.2	65	45	20	93.40	0.06343	1.04E-05	[187]
2	ZnO-Fe₂O₃	Xe lamp	300	0.4	100	60	20	87.50	0.05922	2.80E-06	[188]
3	GODs/TiO₂	Xe lamp	300	0.4	50	60	40	22.00	—	1.41E-06	[189]
4	SnIn₄S₈/CeO₂	Xe lamp	300	0.6	50	150	20	98.80	0.047	8.44E-07	[190]
5	CuS/TiO₂	metal halide lamp	400	1.0	50	210	30	84.70	—	3.49E-07	[191]

order	Aspect	Challenge	Future direction
1	photocatalyst development	developing high efficient Bi-based photocatalysts for Cr(VI) reduction	attempting more modification strategies on Bi-based materials (e.g., microenvironment regulation)
2		expiration time of Bi-based photocatalysts	conducting long-term performance evaluation test for Bi-based materials to demonstrate expiration time development of detection technology to check the potential leakage of nano-metals or toxic metal ions
3		objective assessment metrics	creating more objective and comprehension assessment metrics for the fair comparison of different photocatalysts comparing the best performer of Bi-based materials with other promising candidates to determine the most suitable photocatalysts
4	photocatalytic Cr(VI) reduction system designing and application	complicated industrial wastewater composition	investigation of detailed parameters for treated Cr(VI) containing wastewater, including pH, composition, Cr(VI) concentration etc.
5		confined to lab-scale test	pilot-scale experiment of Bi-based photocatalytic Cr(VI) reduction system
6		energy and cost estimation	lowering the cost of material preparation through massive production or find green and cost-effective synthesis method for the fabrication of Bi-based materials developing Bi-based photocatalysts with excellent optical property to reduce energy consumption by directly utilizing solar energy
7		economical assessment	life cycle assessment to determine the total cost of Bi-based photocatalytic system, from material fabrication, application, and disposal. potential influence to the surrounding environment should be evaluated after the building of photocatalytic Cr(VI) reduction unit.

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