光驱动费托合成中双路径策略实现高选择性烃类产物制备

doi:10.1016/S1872-2067(26)65107-8

催化学报 ›› 2026, Vol. 87: 22-46.DOI: 10.1016/S1872-2067(26)65107-8

光驱动费托合成中双路径策略实现高选择性烃类产物制备

丁扬, 陆义桢, 余天荣, 张明睿, 赵睿, 杨睿杰, 李其鑫, 吴仕群^*(), 张金龙^*()

华东理工大学化学与分子工程学院, 绿色化学与工业催化全国重点实验室, 上海 200237

收稿日期:2025-11-17 接受日期:2026-02-04 出版日期:2026-08-18 发布日期:2026-06-24
通讯作者: ^*电子信箱: wushiqun@ecust.edu.cn (吴仕群),
jlzhang@ecust.edu.cn (张金龙).
基金资助:
国家自然科学基金(22461142136);国家自然科学基金(22202070);国家自然科学基金(22572051);上海市教育委员会创新计划(2021-01-07-00-02-E00106);上海市科学技术委员会(22230780200);上海市科学技术委员会(20DZ2250400);上海市科学技术委员会(2018SHZDZX03);上海市教育发展基金会和上海市教育委员会晨光计划(24CGA30)

Dual pathways in photo-driven Fischer-Tropsch synthesis for high selective hydrocarbon production

Yang Ding, Yizhen Lu, Tianrong Yu, Mingrui Zhang, Rui Zhao, Ruijie Yang, Qixin Li, Shiqun Wu^*(), Jinlong Zhang^*()

State key laboratory of green chemical engineering and industrial catalysis, School of Chemistry and Molecular Engineering, East China University of Science & Technology, Shanghai 200237, China

Received:2025-11-17 Accepted:2026-02-04 Online:2026-08-18 Published:2026-06-24
About author:Shiqun Wu received his Ph.D. degree in 2021 from East China University of Science and Technology under the supervision of Prof. Jinlong Zhang, and subsequently continued his postdoctoral research at the same institution. In 2024, he was appointed as an associate professor at East China University of Science and Technology. His research interests focus on the design and modulation of atomically dispersed active sites in photocatalysts and photothermal catalysis, with applications in the conversion of methane and carbon dioxide. He has published more than 40 peer-reviewed papers. He was invited as a young member of the editorial board of Chin. J. Catal. Since 2025.
Jinlong Zhang received a Ph.D. (1993) in fine chemicals from East China University of Science and Technology. He studied in Osaka Prefecture University as a postdoctor. He became a full professor in 2000. He was selected as Member of Academia Europaea in 2019. He is currently on the Editorial Boards of “Applied Catalysis B: Environmental’ ’and is also the editor of “Res. Chem. Intermed’’. His research interests include photocatalysis, environmental and materials science. He has published more than 600 peer-reviewed papers. He has been selected as the “Most Cited Chinese Researcher” by Elsevier in 2014‒2025, and was awarded as a “Highly Cited Scientist” by Clarivate Analytics in 2018‒2025.
Supported by:
National Natural Science Foundation of China(22461142136);National Natural Science Foundation of China(22202070);National Natural Science Foundation of China(22572051);Innovation Program of Shanghai Municipal Education Commission(2021-01-07-00-02-E00106);Science and Technology Commission of Shanghai Municipality(22230780200);Science and Technology Commission of Shanghai Municipality(20DZ2250400);Science and Technology Commission of Shanghai Municipality(2018SHZDZX03);Chenguang Program of Shanghai Education Development Foundation and Shanghai Municipal Education Commission(24CGA30)

摘要/Abstract

摘要：

在全球能源需求攀升与双碳目标推进的双重背景下,化石能源的碳排放约束成为能源转型的核心约束, 费托合成(FTS)作为非石油路线制备液体燃料的技术路径, 是能源结构调整与碳中和的重要抓手, 可将煤、天然气、生物质等含碳资源转化为具有较高附加值的烃类产物, 有效降低对石油的依赖. 然而, 传统热催化费托合成存在反应条件苛刻(200-500 °C、2-5 MPa)、催化剂易失活、产物选择性受安德森-舒尔茨-弗洛里(ASF)分布严重限制等问题, 且副产物甲烷与二氧化碳生成量大, 碳原子经济性低, 严重制约其清洁应用. 太阳能作为可持续能源, 为解决上述瓶颈提供了新思路, 光驱动费托合成(PFTS)技术凭借温和反应条件、高选择性调控潜力及低能耗优势, 成为能源催化领域的研究热点.

本文聚焦过去十年光驱动费托合成的研究进展, 创新性地将其划分为光诱导热催化与光热协同催化两条核心路径, 系统阐释了不同路径的能量传递机制与调控规律. 在材料设计方面, 系统梳理了活性相构建与晶相调控、载体与界面工程、疏水表面与微环境优化等关键策略: 光诱导热催化通过高效光热转换形成局部高温场, 依托材料的全光谱吸收与快速热转化能力驱动反应进行, 通过表面结构调控优化产物选择性; 载体与界面调控通过异质结构设计、功能掺杂等方式调制界面电荷分布, 强化金属-载体相互作用, 促进反应物吸附活化与中间体转化; 疏水表面设计则通过构建特殊表面结构, 抑制水煤气变换等副反应, 优化反应微环境, 提升目标产物选择性. 光热协同催化则通过光生载流子与热效应的动态耦合实现突破, 光生载流子直接参与反应中间体活化, 调制反应路径以提升选择性, 局部光热场则降低反应能垒, 在温和条件下实现高效CO加氢. 其中, 介孔载体的限域效应、多维载体与多相界面的协同作用、助催化剂引入与动态界面调控, 以及异质结与层状前驱体衍生结构的创新设计, 均有效促进了光生载流子分离迁移与热效应利用, 显著提升了催化活性与产物选择性. 通过对比两条路径, 明确了能量传递方式与光生载流子作用的本质差异, 提炼出抑制甲烷/二氧化碳生成、导向C₂₊烯烃或C₅₊烷烃的选择性调控普适策略, 同时指出热与非热效应定量分离、中间体原位解析等关键研究空白.

综上, 本文通过系统归纳光驱动费托合成的反应机制与材料设计原理, 为光热催化剂的理性设计与开发提供了理论支撑. 未来需结合原位表征技术、非贵金属基催化剂开发及反应器尺度优化等方向, 推动光驱动费托合成从基础研究走向工业化应用, 为含碳资源低碳转化与能源可持续发展提供技术保障.

关键词: 费托合成, 光热催化, 反应机理, 产物选择性调控

Abstract:

Fischer-Tropsch synthesis converts syngas (CO/H₂) to liquid fuels and value-added chemicals, but conventional thermocatalysis requires severe conditions, shows rapid deactivation, and offers limited control over product distributions. This review examines photo-driven Fischer-Tropsch synthesis with a focus on advances reported in the past decade, concentrating on two mechanistic routes: photo-induced thermal catalysis and photothermal synergistic catalysis. We compile progress in materials design that includes support and interface engineering, modulation of the active phase, and rational use of cocatalysts. Pathway control is discussed with emphasis on lowering methane and carbon dioxide formation while steering selectivity to C₂₊ olefins or C₅₊ alkanes under comparatively mild conditions. By contrasting the two routes, the review clarifies differences in energy transduction and the roles of photogenerated charge carriers, and from these differences extracts general principles for selectivity engineering and catalyst stability. Critical gaps are identified, notably quantitative separation of thermal and non-thermal effects, operando elucidation of reaction intermediates, standardized reporting of light and temperature, and long-term durability under realistic feeds. The review closes with research priorities for coupling mechanism-informed catalyst design with thermal management and reactor scale strategies to advance Fischer-Tropsch synthesis toward application.

Key words: Fischer-Tropsch synthesis, Photothermal catalysis, Reaction mechanism, Product selectivity regulation

丁扬, 陆义桢, 余天荣, 张明睿, 赵睿, 杨睿杰, 李其鑫, 吴仕群, 张金龙. 光驱动费托合成中双路径策略实现高选择性烃类产物制备[J]. 催化学报, 2026, 87: 22-46.

Yang Ding, Yizhen Lu, Tianrong Yu, Mingrui Zhang, Rui Zhao, Ruijie Yang, Qixin Li, Shiqun Wu, Jinlong Zhang. Dual pathways in photo-driven Fischer-Tropsch synthesis for high selective hydrocarbon production[J]. Chinese Journal of Catalysis, 2026, 87: 22-46.

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图/表 14

Table 1 Summary of photo-driven catalytic reaction mechanisms.

Mechanism	Core process	Key characteristics
Pure photocatalysis	light-driven generation and direct utilization of electron-hole pairs for redox reactions	relies solely on photoexcitation negligible thermal contribution (near-ambient temperature)
Thermally assisted photocatalysis	photoexcitation as the primary driver, with mild external heating enhancing performance	photo-primary, thermal-auxiliary heating reduces reaction energy barriers & suppresses charge recombination
Photo-induced thermal catalysis	light energy elevates temperature to drive conventional thermal catalysis	thermochemical pathway dominates negligible direct contribution from photogenerated carriers optimized reaction pathway for selectivity control
Photothermal synergistic catalysis	simultaneous and synergistic coupling of photochemical (carrier generation) and thermochemical (heat) pathways	self-supplied heat via photothermal conversion (100-400 °C) supra-additive enhancement beyond the sum of individual effects synergy between thermal acceleration of charge transfer and carrier-induced lowering of activation energies

Fig. 1. Schematic illustrations of the four types of mechanisms in light-driven catalytic conversion.

Fig. 2. (a-d) XPS profiles of different catalysts and operando X-ray adsorption experiments. (a) Ex-situ XPS spectra of Fe5C2 catalyst at different treated conditions. (b) O1s spectra of fresh and used Fe5C2 catalyst. (c) In-situ Fe K-edge XANES of Fe5C2 catalyst under different reaction times (under photoirradiation). (d) In-situ EXAFS of Fe5C2 catalyst under different reaction times (under photo-irradiation). (e) Energy profiles for two CH2 coupling and hydrogenation forming C2H6 on Fe5C2 (111) and Fe5C2 (111)-4Oads, as well as the corresponding intermediate structures. (f) Energy profiles for C2H4 adsorption and hydrogenation forming C2H6 under thermal-driven (ground-state) and photo-driven (excited-state) conditions on Fe5C2 (111)-4Oads and Fe5C2(111) surfaces, as well as the corresponding intermediate structures. (Fe, C, O and H atoms are blue, brown, red, and white, respectively; the C atom is colored black to distinguish it from CH2). Reproduced with permission from Ref. [82]. Copyright 2018, Elsevier. High-resolution XPS spectra of fresh Fe5C2/α-Al2O3 catalyst (g) and spent catalyst (h). 57Fe Mössbauer spectra of fresh Fe5C2/α-Al2O3 (i) and spent catalyst (j). Reproduced with permission from Ref. [83]. Copyright 2020, Springer Nature.

Fig. 3. (a-d) Characterization data for Co-450. (a,b) HRTEM images. (c) HAADF-STEM image. (d) EDX element maps for Co, Zn, Al, and O. The potential energy profile of CO dissociation on Co3O4 (220), Co (111)/Co3O4 (220), and Co (111) (e), CH2 coupling and C2H4 hydrogenation on Co (111)/Co3O4 (220) and Co (111) (f). Reproduced with permission from Ref. [84]. Copyright 2018, Wiley-VCH. (g) UV-vis spectra for Co-x and CoAl-LDH. The calculation models for Co3O4 (220) surface (h) and Co (111) surface (i), and the potential energy profile of CH4 formation (j) and C-C coupling (k) on Co3O4 (220) and Co (111). Reproduced with permission from Ref. [85]. Copyright 2019, Elsevier.

Fig. 4. XPS spectra for Co-C, Co-CN, Co-BCN catalyst: survey spectrum (a) and N 1s (b). (c) The measured work functions (Φ) via UPS analysis. (d) TPD profiles of CO over Co-C, Co-CN and Co-BCN. (e) Pulse CO reactions in a He flow over Co-BCN catalysts at 230 °C. The peaks of CO2 (m/z = 44) and CO (m/z = 28) are shown in the profiles. (f) Steady DRFITS spectra of syngas adsorption on Co-BCN catalysts at 230 °C. Reaction conditions: H2/CO/N2 = 60/20/20 in a total flow of 5 mL min?1 under dry conditions. Reproduced with permission from Ref. [88]. Copyright 2022, Elsevier. (g) High-resolution Fe 2p XPS spectra of Fe5C2 and Fe5C2/NCT samples. (h) Fe K-edge XANES spectra for catalysts. (i) CO-TPD profiles of Fe5C2 and Fe5C2/NC600 samples. (j) Pulse reactions of CO in a flow of He over the Fe5C2/NC600 catalyst at 250 °C. (k) Potential energy profile of H-assisted CO dissociation on Fe5C2 (510) and Fe5C2 (510)/different configurations of N (pyrrolic, pyridinic, and graphitic N). Reproduced with permission from Ref. [89]. Copyright 2022, American Chemical Society. (l) Ni K-edge XANES. (m) Ni K-edge EXAFS spectra for Ni-MMO and Ni-x catalysts. (n) Ni 2p XPS spectra for Ni-MMO and Ni-x catalysts. (o) Potential energy profiles for CH2 coupling and C2H4 hydrogenation on Ni/Al2O3 and Ni/MnO. Reproduced with permission from Ref. [90]. Copyright 2019, Wiley-VCH.

Fig. 5. Potential energy profiles for H-assisted CO hydrogenation to methane (a) and C-C coupling reactions (b) on Ni (111) and 4P/Ni (111). Reproduced with permission from Ref. [91]. Copyright 2021, Wiley‐VCH. (c) CO-TPD profiles for the Co-NP, Ru1Co-SAA and RunCo-NA catalysts. (d) Potential energy profile of CO* dissociation. (e) Potential energy profile of eight C-C coupling paths for C2* intermediates. (f) Energy barriers of different C-C coupling paths with transition state configurations. Color code: Ru (orange), Co (violet), C (grey), H (white). (g) Correlation analysis between the unsaturation of C2* intermediates relative to ethane (Ω) and the energy barrier reduction (ΔEa) of Ru1Co-SAA minus Co-NP. (h) Linear correlation between unsaturation of C2* intermediates relative to ethane (Ω) and energy barrier reduction (ΔEa) of Ru1Co-SAA minus Co-NP. Reproduced with permission from Ref. [60]. Copyright 2023, Springer Nature.

Fig. 6. (a) SEM image for LD-Co/PDVB on a silicon wafer substrate. Photographs of a water droplet on LD-Co (b) and LD-Co/PDVB (c) catalysts. (d) UV-vis diffuse reflectance spectra for ZnCoAl-LDH, LD-Co, PDVB and LD-Co/PDVB. (e) Temperature profiles for LD-Co/PDVB, LD-Co and PDVB under Xe lamp (UV-Vis) irradiation at 1.79 W cm-2. (f) Adsorption isotherms for water vapor at near reaction temperature (200 °C) on the LD-Co and LD-Co/PDVB catalysts. (g) Water vapor partial pressure pulse experiments at 30 °C on the LD-Co and LD-Co/PDVB catalysts. Reproduced with permission from Ref. [94]. Copyright 2023, Elsevier. (h) The contact angle of the obtained catalysts. In-situ FTIR of the Fe/Fe3C (i) and the Fe/Fe3C-c (j) catalysts, respectively. Reproduced with permission from ref. [95]. Copyright 2023, Wiley-VCH.

Table 2 Representative work on photo-induced thermal catalysis mechanistic reactions.

Sample	Actual temperature (°C)	Conditions	Conversion rates (CO)	Selectivity of CO₂	Selectivity* (wt%)	Ref.
Co-450	195	CO:H₂:N₂ = 20:60:20, 0.18 MPa, UV-vis, 300 W Xe lamp	15.4%	47.6%	CH₄: 48%, C₂-C₄=: 36.0%, C₂-C₄o (o/p = 6.1), C₅₊: 10.1%	[84]
O-decorated Fe₅C₂	490	CO:H₂:Ar = 25:50:25, atmospheric pressure, 300 W Xe lamp, 2.9 W cm^-2	49.5%	18.9%	CH₄: 33.1%; C₂-C₄=: 55.5%, C₂-C₄o: 5.1% (o/p = 10.9), C₅₊: 6.3%	[82]
Co-700	210	CO:H₂:N₂ = 20:60:20, 0.18 MPa, UV-vis, 300 W Xe lamp	35.4%	3.1%	CH₄: 35.0%, C₂-C₄: 36.3%, C₅₊: 28.7%	[85]
Ni-500 (Ni:Mn = 2:1)	210	CO:H₂:N₂ = 20:60:20, 0.18 MPa, 300 W Xe lamp, 2.04 W cm^-2	14.9%	0.2%	CH₄: 30.%, C₂-C₄=: 33.0%, C₂-C₄o: 32.1% (o/p = 1.0), C₅₊: 4.1%	[90]
Fe₅C₂/α-Al₂O₃	340	CO:H₂:N₂ = 20:60:20, 0.18 MPa, UV-vis, 300 W Xe lamp, 6.7 W cm^-2	52.5%	not reported (NR)	CH₄: 15.2%, C₂-C₄=: 50.3% (o/p = ~60)	[83]
Co₁Mn_x/(MnO)_2‒_x	250	CO:H₂:N₂=20:20:60, 0.18 MPa, 300 W Xe lamp	13.9%	22.6%	CH₄: 28.4%, C₂-C₄=: 27.0% (o/p = 3.2)	[96]
TiO₂-Ni-P-3	115	CO:H₂:N₂ = 20:60:20, 0.18 MPa, 300 W Xe lamp, 1.82 W cm^-2	20.70%	0.65%	CH₄: 28.65%; C₂-C₄: 41.67%, C₅₊: 29.03%	[91]
α-C30A30	NR	CO:H₂ = 1:3, 55.5 kPa, 300 W Xe lamp	28.8%	NR	CH₄: 24.8%, C₂-C₄=: 71.9% (o/p = 16.7)	[97]
Fe₅C₂/NC600	250	CO:H₂:N₂ = 20:40:40, 0.18 MPa, 300 W Xe lamp, 2.96 W cm^-2	22.3% (±0.5)	16.7% (±1.3)	CH₄: 22.3% (±1.1); C₂-C₄=: 55.3% (±0.4); C₂-C₄o: 5.9% (±0.1) (o/p = 9.4); C₅₊: 16.2% (±1.6)	[89]
Co-BCN	230	CO:H₂:N₂ = 20:60:20, 0.18 MPa, UV-vis, 300 W Xe lamp, 2.8 W cm^-2	44.0%	3.1%	hydrocarbons: 96.9%	[88]
LD-Co/PDVB	195	CO:H₂:N₂ = 20:40:40, 0.2 MPa, 300 W Xe lamp, 1.79 W cm^-2	14.43%	5.17%	CH₄: 33.48%; C₂-C₆=: 42.72%, C₂-C₆o: 18.63% (o/p = 2.3)	[94]
Ru₁Co-SAA	200	CO:H₂:N₂ = 20:40:40, 0.5 MPa, 300 W Xe lamp, 1.80 W cm^-2	58.6%	0.35%	CH₄: 11.2%, C₂-C₄: 12.6%, C₅₊: 75.8%	[60]
CoFe-BCN	264	CO:H₂:N₂ = 20:60:20, 0.18 MPa, 300 W Xe lamp, 2.40 W cm^-2	18.4%	10.5%	CH₄: 28.3%, C₂-C₄: 57.7%, C₅₊: 14.0%	[44]
Fe/Fe₃C-c	340	CO:H₂:N₂ = 20:60:20, 0.18 MPa, 300 W Xe lamp	22.6%	6.5%	CH₄: 21.4%, C₂-C₄=: 48.0%, C₂-C₄o: 4.8% (o/p = 10.1), C₅₊: 19.4%	[95]
Fe₅C₂-350	340	CO:H₂:N₂ = 20:60:20, 0.18 MPa, 300 W Xe lamp	24.3%	5.1%	CH₄: 28.7%, C₂-C₄=: 54.2%, C₂-C₄o: 3.2% (o/p = 16.9), C₅₊: 13.9%	[98]
Ni-r-TiO₂	180	CO:H₂:N₂ = 20:40:40, 0.18 MPa, 300 W Xe lamp (200-1100 nm), 1.84 W cm^-2	23.3%	2.3%	CH₄: 24.7%, C₂₊: 73%	[99]

Table 2 Representative work on photo-induced thermal catalysis mechanistic reactions.

Sample	Actual temperature (°C)	Conditions	Conversion rates (CO)	Selectivity of CO₂	Selectivity* (wt%)	Ref.
Co-450	195	CO:H₂:N₂ = 20:60:20, 0.18 MPa, UV-vis, 300 W Xe lamp	15.4%	47.6%	CH₄: 48%, C₂-C₄=: 36.0%, C₂-C₄o (o/p = 6.1), C₅₊: 10.1%	[84]
O-decorated Fe₅C₂	490	CO:H₂:Ar = 25:50:25, atmospheric pressure, 300 W Xe lamp, 2.9 W cm^-2	49.5%	18.9%	CH₄: 33.1%; C₂-C₄=: 55.5%, C₂-C₄o: 5.1% (o/p = 10.9), C₅₊: 6.3%	[82]
Co-700	210	CO:H₂:N₂ = 20:60:20, 0.18 MPa, UV-vis, 300 W Xe lamp	35.4%	3.1%	CH₄: 35.0%, C₂-C₄: 36.3%, C₅₊: 28.7%	[85]
Ni-500 (Ni:Mn = 2:1)	210	CO:H₂:N₂ = 20:60:20, 0.18 MPa, 300 W Xe lamp, 2.04 W cm^-2	14.9%	0.2%	CH₄: 30.%, C₂-C₄=: 33.0%, C₂-C₄o: 32.1% (o/p = 1.0), C₅₊: 4.1%	[90]
Fe₅C₂/α-Al₂O₃	340	CO:H₂:N₂ = 20:60:20, 0.18 MPa, UV-vis, 300 W Xe lamp, 6.7 W cm^-2	52.5%	not reported (NR)	CH₄: 15.2%, C₂-C₄=: 50.3% (o/p = ~60)	[83]
Co₁Mn_x/(MnO)_2‒_x	250	CO:H₂:N₂=20:20:60, 0.18 MPa, 300 W Xe lamp	13.9%	22.6%	CH₄: 28.4%, C₂-C₄=: 27.0% (o/p = 3.2)	[96]
TiO₂-Ni-P-3	115	CO:H₂:N₂ = 20:60:20, 0.18 MPa, 300 W Xe lamp, 1.82 W cm^-2	20.70%	0.65%	CH₄: 28.65%; C₂-C₄: 41.67%, C₅₊: 29.03%	[91]
α-C30A30	NR	CO:H₂ = 1:3, 55.5 kPa, 300 W Xe lamp	28.8%	NR	CH₄: 24.8%, C₂-C₄=: 71.9% (o/p = 16.7)	[97]
Fe₅C₂/NC600	250	CO:H₂:N₂ = 20:40:40, 0.18 MPa, 300 W Xe lamp, 2.96 W cm^-2	22.3% (±0.5)	16.7% (±1.3)	CH₄: 22.3% (±1.1); C₂-C₄=: 55.3% (±0.4); C₂-C₄o: 5.9% (±0.1) (o/p = 9.4); C₅₊: 16.2% (±1.6)	[89]
Co-BCN	230	CO:H₂:N₂ = 20:60:20, 0.18 MPa, UV-vis, 300 W Xe lamp, 2.8 W cm^-2	44.0%	3.1%	hydrocarbons: 96.9%	[88]
LD-Co/PDVB	195	CO:H₂:N₂ = 20:40:40, 0.2 MPa, 300 W Xe lamp, 1.79 W cm^-2	14.43%	5.17%	CH₄: 33.48%; C₂-C₆=: 42.72%, C₂-C₆o: 18.63% (o/p = 2.3)	[94]
Ru₁Co-SAA	200	CO:H₂:N₂ = 20:40:40, 0.5 MPa, 300 W Xe lamp, 1.80 W cm^-2	58.6%	0.35%	CH₄: 11.2%, C₂-C₄: 12.6%, C₅₊: 75.8%	[60]
CoFe-BCN	264	CO:H₂:N₂ = 20:60:20, 0.18 MPa, 300 W Xe lamp, 2.40 W cm^-2	18.4%	10.5%	CH₄: 28.3%, C₂-C₄: 57.7%, C₅₊: 14.0%	[44]
Fe/Fe₃C-c	340	CO:H₂:N₂ = 20:60:20, 0.18 MPa, 300 W Xe lamp	22.6%	6.5%	CH₄: 21.4%, C₂-C₄=: 48.0%, C₂-C₄o: 4.8% (o/p = 10.1), C₅₊: 19.4%	[95]
Fe₅C₂-350	340	CO:H₂:N₂ = 20:60:20, 0.18 MPa, 300 W Xe lamp	24.3%	5.1%	CH₄: 28.7%, C₂-C₄=: 54.2%, C₂-C₄o: 3.2% (o/p = 16.9), C₅₊: 13.9%	[98]
Ni-r-TiO₂	180	CO:H₂:N₂ = 20:40:40, 0.18 MPa, 300 W Xe lamp (200-1100 nm), 1.84 W cm^-2	23.3%	2.3%	CH₄: 24.7%, C₂₊: 73%	[99]

Fig. 7. (a,b) TEM images of Ru/graphene. The inset in (b) is a HRTEM image of worm-like Ru nanostructures. (c) UV-vis absorption spectra of Ru/graphene and graphene. (d) Arrhenius plots of light-induced FTS reaction and dark reaction. Reproduced with permission from Ref. [104]. Copyright 2015, American Chemical Society. (e) Flow reaction test of 2Co/STO with the different working temperatures under UV light off and on at atmospheric pressure. (f) The solar-driven FTS reaction for C1-C4 production over the 2Co/STO catalyst with and without sacrificial agents (FeCl3 and Na2SO3 were used for quenching the photogenerated electrons and holes, respectively; loading amount, 5 wt%). (g) In-situ DRIFTS spectra of the adsorbed surface species during time evolution under CO and H2 gas with cooperative UV light- and thermal-driven (100 °C) catalysis. (h) By contrast, in-situ DRIFTS spectra of 2Co/SiO2 under the same test conditions. (i) The photocarrier-assisted photothermocatalysis of FTS over the Co/STO catalyst. (j) The main surface intermediates of the reaction pathway. Reproduced with permission from ref. [105]. Copyright 2021, Royal Society of Chemistry.

Fig. 8. ESR spectra of the DMPO-O2•− (a) and DMPO-OH (b) adducts over CoMnC-450 under light irradiation. High-resolution SI-XPS spectra of Co 2p (c) and Mn 2p (d) on CoMnC-450 samples tested in darkness and under illumination. (e,f) In-situ FTIR study of adsorbed CO on the CoMnC-450 catalysts in darkness (i) and under illumination (j). (After exposure to CO for 30 min, then purging by N2 for 10 min). (g) Potential energy profiles for CO hydrogenation under ground states and excited states (thermal- and Photo-Driven catalysis) on Co (111)/MnO (200). Co, Mn, C, O, and H atoms are shown in yellow, cyan, red, gray, and bluish-violet, respectively. Reproduced with permission from Ref. [45]. Copyright 2023, Wiley‐VCH. (h) UV-vis diffuse reflectance absorption spectra. (i) Forbidden bandwidth data. (j) Photocurrent density data under visible light condition. Reproduced with permission from Ref. [109]. Copyright 2024, Wiley‐VCH.

Fig. 9. (a) Co 2p XPS spectra of Co/graphitic carbon material. (b) CO-TPD profiles of Co/T and Co/T-PW catalysts. (c) Photocurrent /T-PW. (d) NH3-TPD results of TaON and TaON-PW. Reproduced with permission from Ref. [113]. Copyright 2023, Royal Society of Chemistry. In situ H2-chemisorption on Cu/CeO2 in the dark (e) or under light irradiation (f), and Co/CeO2 in the dark (g) or under light irradiation (h), at 180 °C. In-situ DRIFTS spectra of CO absorption under dark conditions (i,k) and under irradiation conditions (j,l) at 180 °C over Co/CeO2 or Co-Cu/CeO2. High-resolution XPS of Ce 3d of Co/CeO2 (m) and Co-Cu/CeO2 (n) samples. (o) Diagram of photo-thermal coordination enhancing catalytic activity. Co can produce alcohols via FTS. The electrons of CeO2 transferred to the surface of Co under illumination promoting the adsorption of CO. The LSPR effect of Cu caused by light accelerates the dissociation of hydrogen. The two effects synergistically promote the reaction rate. Reproduced with permission from Ref. [114]. Copyright 2022, Royal Society of Chemistry.

Fig. 10. (a) In-situ XPS spectra of NiAl-MMO and the samples reduced at different temperatures (Ni-x). (b) EXAFS of NiAl-MMO and Ni-x. (c) Catalyst-bed temperature as a function of light irradiation time. The potential-energy profile of the most possible reaction paths for syngas conversion on Ni (111) and 4O/Ni (111): CH4 formation (d) and C-C coupling (e). Reproduced with permission from Ref. [117]. Copyright 2016, Wiley-VCH.

Table 3 Representative work on photothermal synergistic catalysis mechanistic reactions.

Sample	Actual temperature (°C)	Conditions	Conversion rates (CO)	Selectivity of CO₂	Selectivity* (wt%)	Ref.
Ru/graphene	150	CO:H₂ = 1:2, 3.0 MPa, visible light, 300 W Xe lamp, 0.5 W cm^-2	43%	< 1 mol%	CH₄: 2.6%, C₂-C₄: 15.7% (56.4% olefins), C₅₊: 81.7%	[104]
Fe(20%)- mTiO₂	220	CO:H₂ = 1:2, atmospheric pressure	75%-85%	not reported (NR)	see Fig. 6 in the original text for details	[103]
Ni-525	150	CO:H₂:Ar = 20:60:20, 0.08 MPa, 300 W Xe lamp	27.7%	2.7%	CH₄: 38.8%, C₂-C₄: 37.4%, C_5-7: 21.1%	[117]
20% Co/TNT	220	CO:H₂:Ar = 20:10:1, 2.0 MPa, 500 W Hg lamp	63.9%	17.3%	CH₄: 34.6%, C₂-C₄: 22.7% (p/o = 98.6:1.4, C₅₊: 42.7%	[108]
Fe-500	230	CO:H₂:N₂ = 20:60:20, 0.18 MPa, 300 W Xe lamp	20.9%	11.4%	CH₄: 28.6%, C₂-C₄=: 42.4%, C₂-C₄o: 9.0% (o/p = 4.7), C₅₊: 8.6%	[118]
2Co/STO	230	CO:H₂ = 1:2, 55 kPa, 300 W Xe lamp, 0.6 W cm^-2	14%	47.6%	CH₄: 15.2%, C₂-C₄=: 28.1%, C₂-C₄o: 9.1% (o/p = 3.1)	[105]
Co-Cu/CeO₂	180	CO:H₂:He = 5:10:85, 3.0 MPa, 300 W Xe lamp	NR	NR	methane: 3.79%, methanol: 61.62%, ethanol: 25.78%, Propanol: 8.81%	[114]
Fe-Co(5:1)/TiC	350	CO:H₂:Ar = 24:72:4, 0.5 MPa, 350-2500 nm irradiation	30%	NR	C₂-C₃: 32%, C₄₊: 27%	[112]
Co/T-PW	220	CO:H₂:Ar = 32.2:64.6:3.2, 2.0 MPa, 500 W Xe lamp	31%	NR	CH₄: 4%, C₂-C₄: 3%, C₅₊: 93%	[113]
CoMnC-450	210	CO:H₂:N₂ = 20:20:60, 0.18 MPa, 300 W Xe lamp	12.6%	18.2%	CH₄: 22.4%, C₂-C₄=: 36.5%, C₂-C₄o: 7.0% (o/p = 4.7), C₅₊: 34.1%	[45]
Co-TZ	220	CO:H₂ = 1:2, 2.0 MPa, 500 W Xe lamp, 0.2 W cm^-2	63.7%	NR	CH₄: 8.5%; C₂-C₄: 2.5%, C₅₊: 89.0%	[109]

Fig. 11. Photo-driven Fischer-Tropsch synthesis: Features, challenges, and prospects.

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光驱动费托合成中双路径策略实现高选择性烃类产物制备

Dual pathways in photo-driven Fischer-Tropsch synthesis for high selective hydrocarbon production

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