Photocatalytic, electrocatalytic and photoelectrocatalytic conversion of methane to alcohol

doi:10.1016/S1872-2067(24)60212-3

Chinese Journal of Catalysis ›› 2025, Vol. 70: 207-229.DOI: 10.1016/S1872-2067(24)60212-3

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Photocatalytic, electrocatalytic and photoelectrocatalytic conversion of methane to alcohol

Yu Huang^a^,^c^,¹, Lei Zou^a^,^b^,¹, Yuan-Biao Huang^a^,^b^,^c^,^d^,^*(), Rong Cao^a^,^b^,^c^,^d^,^*()

^aState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences, Fuzhou 350002, Fujian, China
^bFujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou 350108, Fujian, China
^cUniversity of Chinese Academy of Sciences, Beijing 100049, China
^dFujian College, University of the Chinese Academy of Sciences, Fuzhou 350002, Fujian, China

Received:2024-10-14 Accepted:2024-12-15 Online:2025-03-18 Published:2025-03-20
Contact: * E-mail: ybhuang@fjirsm.ac.cn (Y.-B. Huang),rcao@fjirsm.ac.cn (R. Cao).
About author:Yuanbiao Huang (Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science) obtained his PhD (2009) under the supervision of Prof. Guo-Xin Jin from Fudan University. In the same year, he joined Prof. Rong Cao's group at FJIRSM, CAS. In 2014, he joined Prof. Qiang Xu's group at AIST (National Institute of Advanced Industrial Science and Technology) as a JSPS (Japan Society for the Promotion of Science) invited fellow. In 2015, he moved back to FJIRSM, CAS and since 2017, he has been a professor at FJIRSM. His research interests include porous framework materials for CO₂ catalysis.
Rong Cao (Fujian Institute of Research on the Structure of Matter，Chinese Academy of Science) received his bachelor’s degree from University of Science and Technology of China in 1986 and obtained his PhD (1993) in FJIRSM (Fujian Institute of Research on the Structure of Matter), Chinese Academy of Sciences. Following post-doctoral experience in the Hong Kong Polytechnic University and JSPS Fellowship in Nagoya University, he became a professor at FJIRSM in 1998. Now, he is the director of FJIRSM. His main research interests include inorganic-organic hybrid materials, nanomaterials and supramolecular chemistry.
¹ Contributed equally to this work.
Supported by:
National Key Research and Development Program of China(2023YFA1507904);National Natural Science Foundation of China(22401280);National Natural Science Foundation of China(U22A20436);National Natural Science Foundation of China(22071245);National Natural Science Foundation of China(22220102005);National Natural Science Foundation of China(22033008);Natural Science Foundation of Fujian Province(2024J08104);Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China(2021ZZ103)

Abstract

Abstract:

The conversion of the greenhouse gas methane to value-added chemicals such as alcohols is a promising technology to mitigate environmental issue and the energy crisis. Especially, the sustainable photocatalytic, electrocatalytic and photoelectrocatalytic conversion of methane at ambient conditions is regarded as an alternative technology to replace with thermocatalysis. In this review, we summarize recent advances in photocatalytic, electrocatalytic and photoelectrocatalytic conversion of methane into alcohols. We firstly introduce the general principles of photocatalysis, electrocatalysis and photoelectrocatalysis. Then, we discuss the mechanism for selective activation of C-H bond and following oxygenation over metal, inorganic semiconductor, organic semiconductor, and heterojunction composite systems in the photocatalytic, electrocatalytic and photoelectrocatalytic methane oxidation in detail. Later, we present insights into the construction of effective photocatalyst, electrocatalyst and photoelectrocatalyst for methane conversion into alcohols from the perspective of band structures and active sites. Finally, the challenges and outlook for future designs of photocatalytic, electrocatalytic and photoelectrocatalytic methane oxidation systems are also proposed.

Key words: Photocatalysis, Electrocatalysis, Photoelectrocatalysis, Methane conversion, Alcohol

Yu Huang, Lei Zou, Yuan-Biao Huang, Rong Cao. Photocatalytic, electrocatalytic and photoelectrocatalytic conversion of methane to alcohol[J]. Chinese Journal of Catalysis, 2025, 70: 207-229.

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Figures/Tables 18

Scheme 1. Conversion system of CH4 photocatalysis, electrocatalysis and photoelectrocatalysis.

Fig. 1. (a) The proposed mechanism of photocatalysis-Fenton reaction for selective CH4 conversion into methanol on P25. Reprinted with permission form Ref. [61]. Copyright 2020, Royal Society of Chemistry. (b) Production of liquid compounds from the partial photooxidation of CH4 after 4 h. Reprinted with permission form Ref. [62]. Copyright 2022, Elsevier. (c) Representative TEM images of q-BiVO4 with scale bars of 2 nm. (d) Selective oxidation of CH4 to HCHO and CH3OH for 7 h under Xe lamp (400 ≤ λ ≤ 780 nm) over q-BiVO4. (e) Proposed reaction mechanism. Reprinted with permission form Ref. [63]. Copyright 2021, Nature.

Fig. 2. (a) Yields of CH3OH in the photocatalytic oxidation of CH4 in systems of WO3/Fe3+ (2 mmol L−1), WO3/Cu2+ (0.1 mmol L−1), WO3/Ag+ (2 mmol L−1), WO3/H2O2 (2 mmol L−1) and WO3 at ∼55 °C under UVC-visible light irradiation. Reprinted with permission form Ref. [65]. Copyright 2015, Elsevier. (b) Production rates of the photocatalytic products aldehyde (CH3CHO) and ethanol (CH3CH2OH) over CeO2-raw and CeO2-x photocatalysts under simulated sunlight irradiation. Reprinted with permission form Ref. [66]. Copyright 2020, Catalysts. (c) Schematic illustration of the nitrate anion intercalation-decomposition (NID) strategy for the exfoliation of BCN into few-layered C3N4 (fl-CN). (d) Comparison of the H2O2 production rate in photocatalytic O2 reduction over the BCN and fl-CN catalysts. (e) Product distribution over the BCN and fl-CN catalysts in photocatalytic oxidation of CH4 with O2. Reprinted with permission form Ref. [67]. Copyright 2024, Wiley-VCH GmbH. (f) The proposed process of different chemical bonds cleavage on the BN surface. (g) Photocatalytic CH4 oxidation performance of BN. Reprinted with permission form Ref. [69]. Copyright 2023, Wiley-VCH GmbH.

Fig. 3. (a) HRTEM images of 2.5%Ag/TiO2 (001). (b) CH3OH selectivity and product yields of Ag-loaded TiO2 photocatalysts with predominantly exposed (001) facets. (c) Proposed photocatalytic mechanism for CH4 oxidation by O2 on the (001) facets of TiO2. Reprinted with permission form Ref. [70]. Copyright 2021, Nature. (d) CH4/O2 ratio-dependent CH4 oxidation on the as-prepared Ag/InGaN photocatalyst in the presence of water. (e) In situ IR spectrum of photocatalytic CH4 oxidation on Ag/InGaN. Reprinted with permission form Ref. [71]. Copyright 2024, Royal Society of Chemistry.

Fig. 4. (a) Product yields and liquid product selectivity at different pressure of CH4. (b) Sketch of the proposed reaction mechanism for photocatalytic CH4 oxidation to CH3OOH, CH3OH, and HCHO. Reprinted with permission form Ref. [72]. Copyright 2019, American Chemical Society. (c) Scheme for the synthetic route of Aux/ZnO (x = 0.08, 0.15,0.30, 0.75, 1.57 and 1.79). (d) Photocatalytic CH4 conversion over different loading amounts of Au on ZnO (Aux/ZnO, x = 0.08, 0.15, 0.30, 0.75, 1.57 and 1.79). Reprinted with permission form Ref. [73]. Copyright 2020, Royal Society of Chemistry. (e) Proposed mechanism of photocatalytic conversion of CH4 to HCHO or CH3OH on Au1/In2O3 or AuNPs/In2O3, respectively. Reprinted with permission form Ref. [74]. Copyright 2023, American Chemical Society.

Fig. 5. (a) Proposed reaction process of photocatalytic CH4 oxidation on Au/TiO2 and Au-CoOx/TiO2 using O2 as the oxidant. (b) Product yields and primary product selectivity on CoOx/TiO2 loaded with or without nanometals after a 2 h reaction. Reprinted with permission form Ref. [75]. Copyright 2020, American Chemical Society. (c) Comparison of the catalytic performance for various photocatalysts. (d) Proposed photocatalytic mechanism for CH4 oxidation over Cu-W-TiO2. Reprinted with permission form Ref. [76]. Copyright 2022, American Chemical Society. (e) Schematic illustration of photocatalytic CH4 conversion over Au0.2Cu0.15-ZnO photocatalysts. (f) Photocatalytic direct CH4 the conversion and the selectivity of the primary products on Aux-ZnO. (g) Photocatalytic direct CH4 the conversion and the selectivity of the primary products on Au0.2Cuy-ZnO. Reprinted with permission form Ref. [77]. Copyright 2022, American Chemical Society. (h) Photocatalytic CH4 conversion over AuPd/ZnO with varied molar ratio of Au to Pd. Reprinted with permission form Ref. [78]. Copyright 2024, Wiley-VCH GmbH.

Fig. 6. (a) Reaction energy profile of CH4 to CH3OH over Au1/WO3 and AuPs/WO3. (b) Comparison of photocatalytic CH4 oxidation products of under visible light (λ ≥ 420 nm) at room temperature (25 °C). (c) Corresponding yields of CH3OH per mole of Au over WO3, AuPs/WO3, and Au1/WO3 catalysts. Reprinted with permission form Ref. [79]. Copyright 2022, Elsevier. (d) Band energy diagram of 2DT, Pd1/2DT, and 3DT (P25). (e) Activity of Pd1/2DT for CH4 oxidation. (f) Proposed catalytic mechanism for the oxidation of methane to methanol. Reprinted with permission form Ref. [80]. Copyright 2021, American Chemical Society.

Fig. 7. (a) Scheme of the photoactivation of different components in the Bi-V-HBEA photocatalyst. (b) CH3OH and C2H6 productivity obtained with the three samples HBEA, V-HBEA, and Bi-V-HBEA at different times during the photocatalytic tests. Reprinted with permission form Ref. [82]. Copyright 2017, American Chemical Society. (c) View of the structure of PMOF-RuFe(OH) incorporating mono-iron hydroxyl. (d) Schematic showing synergic catalysis in PMOF-RuFe(OH) for selective photo-activation of the C-H bond in CH4 to CH3OH in the presence of oxygen and water. (e) Comparison of the catalytic activity for photo-oxidation of CH4 to CH3OH over PMOF-RuFe(OH) with other photocatalysts. (f) Calculated energy profiles for the activation of C-H bond in CH4 over confined mono-iron hydroxyl sites. Reprinted with permission form Ref. [83]. Copyright 2022, Nature.

Fig. 8. (a) Proposed reaction scheme for photocatalytic conversion of CH4. (b) Photocatalytic activities for conversion of CH4 of the samples at CH4 (1000 ppm) and pure air atmosphere under irradiation of full spectrum light: the yield of CH3OH for the pure g-C3N4, 10CW, 30CW, 70CW, and pure Cs0.33WO3 samples. Reprinted with permission form Ref. [86]. Copyright 2019, American Chemical Society. (c) Schematic of the photocatalytic CH4 oxidation to ethanol by the hollow CeO2@PdO@FeOx nanosphere photocatalyst. (d) Photocatalytic production rates of liquid and gas products over CeO2, CeO2@PdO, and CeO2@PdO@FeOx. (e) ΔG of the *CH3-*CO coupling on PdFe-PdCe sites with different *CO coverages. Reprinted with permission form Ref. [88]. Copyright 2024, American Chemical Society. (f) 2D in-plane Z-scheme heterostructures composed of two different metal oxides and conventional single metal oxide semiconductor for selective CH4 photooxidation. (g) Free energy diagrams for CH4 oxidation over the ZnO/Fe2O3 porous nanosheet slab and the ZnO porous nanosheet slab. (h) Product yield over the ZnO/Fe2O3 porous nanosheets and the ZnO porous nanosheets. Reprinted with permission form Ref. [89]. Copyright 2022, American Chemical Society.

Table 1 Summary of photocatalytic CH4 oxidation to alcohol.

Sample	Wavelength (nm)	Product	Activity	Selectivity (%)	Ref.
TiO₂	Full-spectrum	CH₃OH	471 μmol g⁻¹ h⁻¹	83	[61]
Bi₂O₃	380 ≤ λ ≤ 760	CH₃OH	3771 μmol g⁻¹ h⁻¹	65	[62]
q-BiVO₄	300 ≤ λ ≤ 600	CH₃OH	766.7 μmol g⁻¹ h⁻¹	92.8	[63]
WO₃	λ ≥185	CH₃OH	67.5 μmol g⁻¹ h⁻¹	37.4	[65]
CeO₂	Full-spectrum	C₂H₅OH	11.4 µmol g_cat⁻¹ h⁻¹	91.5	[66]
fl-CN-530	300 ≤ λ ≤ 780	CH₃OH	12.3 µmol	50.8	[67]
Ag/TiO₂	300 ≤ λ ≤ 500	CH₃OH	4.8 mmol g⁻¹ h⁻¹	80	[70]
Ag/InGaN	Full-spectrum	CH₃OH	45.5 mmol g⁻¹ h⁻¹	93.3	[71]
Au/ZnO	300 ≤ λ ≤ 500	CH₃OH	2.06 mmol g⁻¹ h⁻¹	15.67	[72]
Au_0.75/ZnO	Full-spectrum	CH₃OH	1.37 mmol g⁻¹	99.1	[73]
AuNPs/In₂O₃	300 ≤ λ ≤ 1100	CH₃OH	1.98 mmol g⁻¹ h⁻¹	89.4	[74]
Au-CoO_x/TiO₂	300 ≤ λ ≤ 500	CH₃OH CH₃OOH	2.54 mmol g⁻¹ h⁻¹	95	[75]
Cu-W-TiO₂	350 ≤ λ ≤ 760	CH₃OH CH₃OOH	8.66 mmol g⁻¹ h⁻¹	50.2	[76]
Au_0.2Cu_0.15- ZnO	Full-spectrum	CH₃OOH CH₃OH	8888 μmol g⁻¹ h⁻¹	~80	[77]
Au₉Pd₁/ZnO	λ ≥ 380	CH₃OH	6267 µmol g⁻¹ h⁻¹	46.7	[78]
Au₁/WO₃	λ ≥ 420	CH₃OH	589 µmol g⁻¹ h⁻¹	75	[79]
Pd1/2DT	λ ≥ 420	CH₃OH	43.75 µmol g⁻¹ h⁻¹	94	[80]
Bi-V-HBEA	UV light	CH₃OH	10.7 µmol g⁻¹ h⁻¹	6.4	[82]
PMOF- RuFe(OH)	400 ≤ λ ≤ 780	CH₃OH	8.81 ± 0.34 mmol g_cat⁻¹ h⁻¹	~100	[83]
Fe@PCN-222	λ ≥ 420	CH₃OH	310 µmol g⁻¹ h⁻¹	28.84	[84]
TiO₂/TiOF₂	380 ≤ λ ≤ 760	CH₃OH	0.7527 µmol g⁻¹ h⁻¹	—	[85]
CeO₂@PdO @FeO_x	Full-spectrum	C₂H₅OH	728 μmol g⁻¹ h⁻¹	>85	[88]
ZnO/Fe₂O₃	Full-spectrum	CH₃OH	178.3 μmol⁻¹ g_cat⁻¹	~100	[89]

Fig. 9. (a) Amounts of CH4 oxidation products generated in the EMOR reactor versus reaction time. Reprinted with permission form Ref. [92]. Copyright 2019, American Chemical Society. (b) Product selectivity after 10, 20, 40, 60, 90, and 120 min of CH4 electrochemical conversion by Rh/Al2O3 modified with NH4BF4. (c) Product selectivity after 20, 40, 60, 90, and 120 min of CH4 electrochemical conversion by Cu/Al2O3 modified with NH4BF4. (d) The schematic mechanism for the formation of Brønsted acid sites on the catalyst surface. Reprinted with permission form Ref. [93]. Copyright 2023, Elsevier. (e) A scheme depicting the preparation of a Fe-N-C SAC. (f) The selectivity of oxygenate products at various potentials. Reprinted with permission form Ref. [94]. Copyright 2023, The Royal Society of Chemistry.

Fig. 10. (a) Production yield rates and ethanol selectivity. (b) Reaction energy profiles for CH4 electrocatalytic oxidation to ethanol on the surfaces of WO3 and Ov-WO3 respectively. Reprinted with permission form Ref. [95]. Copyright 2023, Elsevier. (c) The average formation rate and total FE of the generated oxygenates at different current density for 0.5 h. (d) Side views of the optimized configurations of the V2O5 (001) and Ov-V2O5(001) surfaces. Reprinted with permission form Ref. [96]. Copyright 2023, Elsevier. (e) Illustration of the formation of CoyNi1-y-Fe2 PBA and its derived catalysts. (f) After electrolysis for two hours at different electrode potentials, the product yield of CH3OH and 2-propanol. (g) FE of CH3OH and 2-propanol. Reprinted with permission form Ref. [97]. Copyright 2022, The Royal Society of Chemistry.

Fig. 11. (a) Schematic illustration of synthesis procedures of Rh/ZnO nanosheets and electrochemical oxidation of CH4 to C2H5OH. (b) FE of C2H5OH for ZnO and x% Rh/ZnO (x = 0.3, 0.6, 1.0) under different applied potentials. Reprinted with permission form Ref. [99]. Copyright 2021, American Chemical Society. (c) A possible scheme for the catalytic conversion of CH4 into CH3OH on NiO-V2O5/Rh catalyst. Reprinted with permission form Ref. [100]. Copyright 2020, Elsevier. (d) FEs and (e) yields of the anodic products C2H5OH and CH3OH over NiO/Ni catalysts at various applied potentials. (f) Calculated reaction energy profiles for CH4 electrooxidation to form C2H5OH and CH3OH at the NiO (200)/Ni (111) interface. The insets: the transition state (TS) structures for CH3OH* and CH2* formations. Colors: Ni (blue), O (red), and H (white). Reprinted with permission form Ref. [101]. Copyright 2020, Elsevier. (g) Schematic illustration of electrocatalytic CH4 conversion using a NiO@NiHF anode. Reprinted with permission form Ref. [102]. Copyright 2020, Elsevier.

Fig. 12. (a) Energy level diagram for the NiO/ZnO heterojunction. (b) Selectivity for oxygenates with NiO/ZnO nanorod catalysts of various lengths. Reprinted with permission form Ref. [103]. Copyright 2023, Elsevier. (c) Production efficiencies of the products of 1-propanol, 2-propanol, and acetaldehyde at different reaction times. (d) Reaction mechanism analysis. Reprinted with permission form Ref. [104]. Copyright 2017, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. (e) Fabrication of the ZrO2 NT/Co3O4 catalyst. (f) Production rate after 3, 6 and 12 h at 1.6 V (vs. RHE). Reprinted with permission form Ref. [105]. Copyright 2021, Elsevier. (g) The corresponding activation energy vs reaction coordinate, (h) the 2p density of states of surface O of the Fermi level, (i) the charge density difference of the ZrO2:Cu2O(111) system. Reprinted with permission form Ref. [107]. Copyright 2021, Elsevier.

Table 2 Summary of electrocatalytic CH4 oxidation to liquid products.

Sample	Electrolyte	Potential	Product	Activity	Selectivity (%)	FE (%)	Ref.
Cu/Al₂O₃	KHCO₃ (0.5 mol L⁻¹)	2 V_Pt	C₂H₅OH	37.14 μmol h⁻¹ cm⁻²	85	90	[93]
Fe-N-C	KOH (0.1 mol L⁻¹)	1.6 V_RHE	C₂H₅OH	4668.3 μmol g_cat⁻¹ h⁻¹	85	68	[94]
O_v-WO₃	0.1 mol L⁻¹ Na₂SO₄ (pH = 2)	1.2 V_RHE	C₂H₅OH	125090 μmol g_cat⁻¹ h⁻¹	99.4	50.7	[95]
O_v-V₂O₅	[BMIM]BF₄	1.15 V_Ag/Ag⁺	CH₃OH	352.5 μmol g_cat⁻¹ h⁻¹	>70	61.1	[96]
Co_yNi_1-_yFe₂O₄	Na₂SO₄ (0.1 mol L⁻¹)	0.8 V_Ag/AgCl	CH₃OH	1925.4 μmol g_cat⁻¹ h⁻¹	82.8	9.03	[97]
LaCo_0.5Fe_0.5O₃	[BMIM]BF₄	0.8 V_Ag/AgCl	CH₃OH	39.3 μmol g_cat⁻¹ h⁻¹	—	92.4	[98]
Rh/ZnO	KOH (0.1 mol L⁻¹)	2.2 V_RHE	C₂H₅OH	789 μmol g_cat⁻¹ h⁻¹	85	22.5	[99]
NiO-V₂O₅/Rh	—	—	CH₃OH	0.65 mol g⁻¹ h⁻¹	97.9	91	[100]
NiO/Ni	NaOH (0.1 mol L⁻¹)	1.4 V_RHE	C₂H₅OH	25 μmol g_NiO⁻¹ h⁻¹	87	89	[101]
NiO@NiHF	NaOH (0.1 mol L⁻¹)	1.46 V_RHE	C₂H₅OH	—	—	85	[102]
NiO/ZnO	Na₂CO₃ (0.5 mol L⁻¹)	1.5 V_SCE	C₂H₅OH	1084.2 μmol g_NiO⁻¹ h⁻¹	81	—	[103]
Co₃O₄/ZrO₂	Na₂CO₃ (0.5 mol L⁻¹)	2 V_RHE	C₃H₇OH	3255.7 μmol g⁻¹ h⁻¹ 3205.5μmol g⁻¹ h⁻¹	>60	—	[104]
ZrO₂ NT/Co₃O₄	Na₂CO₃ (0.5 mol L⁻¹)	1.6 V_RHE	C₃H₇OH	2416 μmol g_cat⁻¹ h⁻¹	>92	—	[105]
ZrO₂:NiCo₂O₄	Na₂CO₃ (0.5 mol L⁻¹)	2 V_Pt	C₃H₇OH	2500 μmol g_cat⁻¹ h⁻¹	>90	—	[106]

Fig. 13. (a) The atomic structures of •OH adsorption on twinning W atoms of (010) facet, (100) facet and (001) facet. (b) Production rate of EG produced in photoelectrocatalytic CH4 conversion on WO3 photoanodes with different (010) facet ratios at a range of potentials under 100 mWcm-2 illumination. (c) Schematic illustration of the proposed reaction mechanism for photoelectrocatalytic CH4 conversion into EG. Reprinted with permission form Ref. [108]. Copyright 2021, Wiley-VCH GmbH. (d) Production yields of S200/30-15 at different potentials (e) Reaction energy of Ov-activated CH3OH to CH2OH and (f) CH4 to CH3 on the WO3 + Ov (100) slab, respectively. Reprinted with permission form Ref. [109]. Copyright 2023, Elsevier. (g) FE for bare (blank) and reduced (shaded) WO3 NTs electrodes. (h) Free energy diagram of water decomposition on the WO3 (100) surface at pH = 2 and 0.7 V vs. RHE. (i) Schematic depicting the overall band diagrams of bare and reduced WO3 NTs. Reprinted with permission form Ref. [110]. Copyright 2023, American Chemical Society.

Fig. 14. (a) Stepwise synthetic procedure and structure of ZnO/graphene/PANI composite. (b) Yields of CH3OH in the photoelectrocatalytic oxidation of CH4 with catalyst of ZnO NWAs, ZnO/graphene, ZnO/PANI, and ZnO/graphene/PANI composites under simulated sunlight illumination. Reprinted with permission form Ref. [112]. Copyright 2019, Chinese Physical Society. (c) Total production of liquid chemicals from partial oxidation of CH4 of different electrodes consisting of as-synthesized SnO2-rutile, commercial TiO2-anatase, and as-synthesized TiO2:SnO2 heterostructure induced by photocatalysis (P), electrocatalysis (E), and photoelectrocatalysis (PE) sources. Reprinted with permission form Ref. [113]. Copyright 2023, Elsevier.

Table 3 Summary of photoelectrocatalyst for CH4 oxidation to alcohol products.

Sample	Wavelength (nm)	Potential	Product	Activity	Selectivity (%)	Ref.
WO₃	simulated solar	1.3 V_RHE	(CH₂OH)₂	0.47 mmol cm⁻² h⁻¹	66	[108]
WO₃ NSs	—	0.9 V_RHE	C₂H₅OH	98900 μmol g_cat⁻¹ h⁻¹	92	[109]
WO₃ NTs	300 ≤ λ ≤ 800	0.7 V_RHE	CH₃OH	0.174 μmol cm⁻² h⁻¹	69.4	[110]
ZnO/Au NWAs	400 ≤ λ ≤ 1100	1.0 V_Ag/AgCl	CH₃OH	1.688 μmol mL⁻¹ h⁻¹	—	[111]
ZnO/graphene/PANI	400 ≤ λ ≤ 1100	1.0 V_Ag/AgCl	CH₃OH	0.49 μmol mL⁻¹ h⁻¹	—	[112]
TiO₂:SnO₂	—	1.3 V_Ag/AgCl	CH₃OH	30 μmol cm⁻² h⁻¹	—	[113]

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Photocatalytic, electrocatalytic and photoelectrocatalytic conversion of methane to alcohol

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