Abstract
Developing a smart material for simultaneous addressal of environmental and energy problems is always a challenge. In an effort to improve the photocatalytic efficiencies, most of photocatalysis research revolve around factors such as charge transfer dynamics, light harvesting, and interface reactions. As well known before, heterogeneous catalysts of different sizes, such as single atoms, nanoclusters, and nanoparticles, show contrasting photocatalytic behavior and activity. Single-atom photocatalysts display tremendous potential in this regard, with excellent optoelectronics and adsorptive properties. However, a better understanding on these material properties is still needed to unveil the working mechanisms for consolidating the photocatalytic theory. This is important, as the active sites on photocatalysts usually have different affinities for reactants, products, and the intermediates involved with the photocatalytic reactions. To this end, the material properties can have a significant impact on catalytic activity and selectivity of the process, thereby changing the pathway of a reaction. A combination of advanced in situ characterizations and theoretical studies can undoubtedly have a crucial role in this journey. In the current chapter, we start with the definition of single-atom photocatalysts and continue the discussion on metal-support interactions with recent developments. Different fabrication techniques of single-atom photocatalysts for effective functioning have been reviewed. Followed by this, a summary of available characterizations for single-atom photocatalysts is presented with structure-activity relationships. Furthermore, the applications in energy and environmental sectors alongside its uniqueness in enhancing the heterogeneous photocatalytic efficiencies were demonstrated. The challenges and future potentials involved in single-atom photocatalysts were highlighted for the development of this field in the new directions.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Similar content being viewed by others
References
Bhattacharyya K, Datta A (2019) Visible light driven efficient metal free single atom catalyst supported on nanoporous carbon nitride for nitrogen fixation. Phys Chem Chem Phys 21:12346–12352. https://doi.org/10.1039/c9cp00997c
Cao Y, Chen S, Luo Q, Yan H, Lin Y, Liu W, Cao L, Lu J, Yang J, Yao T, Wei S (2017) Atomic-level insight into optimizing the hydrogen evolution pathway over a Co 1-N 4 single-site photocatalyst. Angew Chem 129:12359–12364. https://doi.org/10.1002/ange.201706467
Cao S, Li H, Tong T, Chen HC, Yu A, Yu J, Chen HM (2018a) Single-atom engineering of directional charge transfer channels and active sites for photocatalytic hydrogen evolution. Adv Funct Mater 28:1–9. https://doi.org/10.1002/adfm.201802169
Cao Y, Wang D, Lin Y, Liu W, Cao L, Liu X, Zhang W, Mou X, Fang S, Shen X, Yao T (2018b) Single Pt atom with highly vacant d-orbital for accelerating photocatalytic H2 evolution. ACS Appl Energy Mater 1:6082–6088. https://doi.org/10.1021/acsaem.8b01143
Chen Y, Huang Z, Ma Z, Chen J, Tang X (2017) Fabrication, characterization, and stability of supported single-atom catalysts. Cat Sci Technol 7:4250–4258. https://doi.org/10.1039/c7cy00723j
Cheng N, Sun X (2017) Single atom catalyst by atomic layer deposition technique. Cuihua Xuebao/Chinese J Catal 38:1508–1514. https://doi.org/10.1016/S1872-2067(17)62903-6
Cheng N, Stambula S, Wang D, Banis MN, Liu J, Riese A, Xiao B, Li R, Sham TK, Liu LM, Botton GA, Sun X (2016) Platinum single-atom and cluster catalysis of the hydrogen evolution reaction. Nat Commun 7:1–9. https://doi.org/10.1038/ncomms13638
Cheng M, Xiao C, Xie Y (2019a) Photocatalytic nitrogen fixation: the role of defects in photocatalysts. J Mater Chem A 7:19616–19633. https://doi.org/10.1039/c9ta06435d
Cheng N, Zhang L, Doyle-Davis K, Sun X (2019b) Single-atom catalysts: from design to application. Springer, Singapore
Choi CH, Lin L, Gim S, Lee S, Kim H, Wang X, Choi W (2018) Polymeric carbon nitride with localized aluminum coordination sites as a durable and efficient photocatalyst for visible light utilization. ACS Catal 8:4241–4256. https://doi.org/10.1021/acscatal.7b03512
Dai Y, Li H (2020) Proton-assisted electron transfer and hydrogen-atom diffusion in a model system for photocatalytic hydrogen production. Commun Mater 1–9. https://doi.org/10.1038/s43246-020-00068-0
Darby MT, Sykes ECH, Michaelides A, Stamatakis M (2018a) Carbon monoxide poisoning resistance and structural stability of single atom alloys. Top Catal 61:428–438. https://doi.org/10.1007/s11244-017-0882-1
Darby MT, Stamatakis M, Michaelides A, Sykes ECH (2018b) Lonely atoms with special gifts: breaking linear scaling relationships in heterogeneous catalysis with single-atom alloys. J Phys Chem Lett 9:5636–5646. https://doi.org/10.1021/acs.jpclett.8b01888
Di J, Chen C, Yang SZ, Chen S, Duan M, Xiong J, Zhu C, Long R, Hao W, Chi Z, Chen H, Weng YX, Xia J, Song L, Li S, Li H, Liu Z (2019) Isolated single atom cobalt in Bi3O4Br atomic layers to trigger efficient CO2 photoreduction. Nat Commun 10:1–7. https://doi.org/10.1038/s41467-019-10392-w
Ding J, Liu X, Shi M, Li T, Xia M, Du X, Shang R, Gu H, Zhong Q (2019) Single-atom silver–manganese catalysts for photocatalytic CO2 reduction with H2O to CH4. Sol Energy Mater Sol Cells 195:34–42. https://doi.org/10.1016/j.solmat.2019.02.009
Du XL, Wang XL, Li YH, Wang YL, Zhao JJ, Fang LJ, Zheng LR, Tong H, Yang HG (2017) Isolation of single Pt atoms in a silver cluster: forming highly efficient silver-based cocatalysts for photocatalytic hydrogen evolution. Chem Commun 53:9402–9405. https://doi.org/10.1039/c7cc04061j
Fang X, Shang Q, Wang Y, Jiao L, Yao T, Li Y, Zhang Q, Luo Y, Jiang HL (2018) Single Pt atoms confined into a metal–organic framework for efficient photocatalysis. Adv Mater 30:1–7. https://doi.org/10.1002/adma.201705112
Gao G, Jiao Y, Waclawik ER, Du A (2016) Single atom (Pd/Pt) supported on graphitic carbon nitride as an efficient photocatalyst for visible-light reduction of carbon dioxide. J Am Chem Soc 138:6292–6297. https://doi.org/10.1021/jacs.6b02692
Gao C, Chen S, Wang Y, Wang J, Zheng X, Zhu J, Song L, Zhang W, Xiong Y (2018) Heterogeneous single-atom catalyst for visible-light-driven high-turnover CO2 reduction: the role of electron transfer. Adv Mater 30:1–9. https://doi.org/10.1002/adma.201704624
Gao C, Low J, Long R, Kong T, Zhu J, Xiong Y (2020) Heterogeneous single-atom photocatalysts: fundamentals and applications. Chem Rev. https://doi.org/10.1021/acs.chemrev.9b00840
Guo XW, Chen SM, Wang HJ, Zhang ZM, Lin H, Song L, Lu TB (2019) Single-atom molybdenum immobilized on photoactive carbon nitride as efficient photocatalysts for ambient nitrogen fixation in pure water. J Mater Chem A 7:19831–19837. https://doi.org/10.1039/c9ta06653e
Hannagan RT, Giannakakis G, Flytzani-Stephanopoulos M, Sykes ECH (2020) Single-atom alloy catalysis. Chem Rev. https://doi.org/10.1021/acs.chemrev.0c00078
He T, Chen S, Ni B, Gong Y, Wu Z, Song L, Gu L, Hu W, Wang X (2018) Zirconium-porphyrin-based metal-organic framework hollow nanotubes for immobilization of noble-metal single atoms. Angew Chemie 130:3551–3556. https://doi.org/10.1002/ange.201800817
Hoque MA, Guzman MI (2018) Photocatalytic activity: experimental features to report in heterogeneous photocatalysis. Materials (Basel) 11. https://doi.org/10.3390/ma11101990
Huang P, Huang J, Pantovich SA, Carl AD, Fenton TG, Caputo CA, Grimm RL, Frenkel AI, Li G (2018a) Selective CO2 reduction catalyzed by single cobalt sites on carbon nitride under visible-light irradiation. J Am Chem Soc 140:16042–16047. https://doi.org/10.1021/jacs.8b10380
Huang P, Liu W, He Z, Xiao C, Yao T, Zou Y, Wang C, Qi Z, Tong W, Pan B, Wei S, Xie Y (2018b) Single atom accelerates ammonia photosynthesis. Sci China Chem 61:1187–1196. https://doi.org/10.1007/s11426-018-9273-1
Jiao L, Jiang HL (2019) Metal-organic-framework-based single-atom catalysts for energy applications. Chem 5:786–804. https://doi.org/10.1016/j.chempr.2018.12.011
Jin X, Wang R, Zhang L, Si R, Shen M, Wang M, Tian J, Shi J (2020) Electron configuration modulation of nickel single atoms for elevated photocatalytic hydrogen evolution. Angew Chem 132:6894–6898. https://doi.org/10.1002/ange.201914565
Kolar JL (2000) Alternative energy technologies. Environ Qual Manag 10:45–54. https://doi.org/10.1002/1520-6483(200024)10:2<45::AID-TQEM6>3.0.CO;2-P
Lee J, Farha OK, Roberts J, Scheidt KA, Nguyen ST, Hupp JT (2009) Metal-organic framework materials as catalysts. Chem Soc Rev 38:1450–1459. https://doi.org/10.1039/b807080f
Lee BH, Park S, Kim M, Sinha AK, Lee SC, Jung E, Chang WJ, Lee KS, Kim JH, Cho SP, Kim H, Nam KT, Hyeon T (2019) Reversible and cooperative photoactivation of single-atom Cu/TiO2 photocatalysts. Nat Mater 18:620–626. https://doi.org/10.1038/s41563-019-0344-1
Li R (2018) Photocatalytic nitrogen fixation: an attractive approach for artificial photocatalysis. Cuihua Xuebao/Chin J Catal 39:1180–1188. https://doi.org/10.1016/S1872-2067(18)63104-3
Li R, Li C (2017) Photocatalytic water splitting on semiconductor-based photocatalysts, 1st ed. Elsevier
Li X, Bi W, Zhang L, Tao S, Chu W, Zhang Q, Luo Y, Wu C, Xie Y (2016) Single-atom Pt as Co-catalyst for enhanced photocatalytic H2 evolution. Adv Mater 28:2427–2431. https://doi.org/10.1002/adma.201505281
Li X, Yang X, Zhang J, Huang Y, Liu B (2019a) In situ/operando techniques for characterization of single-atom catalysts. ACS Catal 9:2521–2531. https://doi.org/10.1021/acscatal.8b04937
Li J, Huang H, Liu P, Song X, Mei D, Tang Y, Wang X, Zhong C (2019b) Metal-organic framework encapsulated single-atom Pt catalysts for efficient photocatalytic hydrogen evolution. J Catal 375:351–360. https://doi.org/10.1016/j.jcat.2019.06.024
Li J, Guan Q, Wu H, Liu W, Lin Y, Sun Z, Ye X, Zheng X, Pan H, Zhu J, Chen S, Zhang W, Wei S, Lu J (2019c) Highly active and stable metal single-atom catalysts achieved by strong electronic metal-support interactions. J Am Chem Soc 141:14515–14519. https://doi.org/10.1021/jacs.9b06482
Li Y, Li B, Zhang D, Cheng L, Xiang Q (2020a) Crystalline carbon nitride supported copper single atoms for photocatalytic CO2 reduction with nearly 100% CO selectivity. ACS Nano 14:10552–10561. https://doi.org/10.1021/acsnano.0c04544
Li J, Liu P, Tang Y, Huang H, Cui H, Mei D, Zhong C (2020b) Single-atom Pt-N3 sites on the stable covalent triazine framework nanosheets for photocatalytic N2 fixation. ACS Catal 10:2431–2442. https://doi.org/10.1021/acscatal.9b04925
Ling C, Niu X, Li Q, Du A, Wang J (2018) Metal-free single atom catalyst for N2 fixation driven by visible light. J Am Chem Soc. https://doi.org/10.1021/jacs.8b07472
Ling C, Ouyang Y, Li Q, Bai X, Mao X, Du A, Wang J (2019) A general two-step strategy–based high-throughput screening of single atom catalysts for nitrogen fixation. Small Methods 3:1–8. https://doi.org/10.1002/smtd.201800376
Liu L, Corma A (2018) Metal catalysts for heterogeneous catalysis: from single atoms to nanoclusters and nanoparticles. Chem Rev 118:4981–5079. https://doi.org/10.1021/acs.chemrev.7b00776
Liu Q, Zhang Z (2019) Platinum single-atom catalysts: a comparative review towards effective characterization. Cat Sci Technol 9:4821–4834. https://doi.org/10.1039/c9cy01028a
Liu W, Cao L, Cheng W, Cao Y, Liu X, Zhang W, Mou X, Jin L, Zheng X, Che W, Liu Q, Yao T, Wei S (2017) Single-site active cobalt-based photocatalyst with a long carrier lifetime for spontaneous overall water splitting. Angew Chem 129:9440–9445. https://doi.org/10.1002/ange.201704358
Liu J, Bunes BR, Zang L, Wang C (2018) Supported single-atom catalysts: synthesis, characterization, properties, and applications. Environ Chem Lett 16:477–505. https://doi.org/10.1007/s10311-017-0679-2
Liu X, Duan X, Wei W, Wang S, Ni BJ (2019a) Photocatalytic conversion of lignocellulosic biomass to valuable products. Green Chem 21:4266–4289. https://doi.org/10.1039/c9gc01728c
Liu L, Wu X, Wang L, Xu X, Gan L, Si Z, Li J, Zhang Q, Liu Y, Zhao Y, Ran R, Wu X, Weng D, Kang F (2019b) Atomic palladium on graphitic carbon nitride as a hydrogen evolution catalyst under visible light irradiation. Commun Chem 2:2–9. https://doi.org/10.1038/s42004-019-0117-4
Liu S, Wang Y, Wang S, You M, Hong S, Wu TS, Soo YL, Zhao Z, Jiang G, Qiu J, Wang B, Sun Z (2019c) Photocatalytic fixation of nitrogen to ammonia by single Ru atom decorated TiO2 nanosheets. ACS Sustain Chem Eng 7:6813–6820. https://doi.org/10.1021/acssuschemeng.8b06134
Long R, Li Y, Liu Y, Chen S, Zheng X, Gao C, He C, Chen N, Qi Z, Song L, Jiang J, Zhu J, Xiong Y (2017) Isolation of Cu atoms in Pd lattice: forming highly selective sites for photocatalytic conversion of CO2 to CH4. J Am Chem Soc 139:4486–4492. https://doi.org/10.1021/jacs.7b00452
Low J, Cheng B, Yu J (2017) Surface modification and enhanced photocatalytic CO2 reduction performance of TiO2: a review. Appl Surf Sci 392:658–686. https://doi.org/10.1016/j.apsusc.2016.09.093
Lu M, Li Q, Liu J, Zhang FM, Zhang L, Wang JL, Kang ZH, Lan YQ (2019) Installing earth-abundant metal active centers to covalent organic frameworks for efficient heterogeneous photocatalytic CO2 reduction. Appl Catal B Environ 254:624–633. https://doi.org/10.1016/j.apcatb.2019.05.033
Lv X, Wei W, Li F, Huang B, Dai Y (2019) Metal-free B@ g-CN: visible/infrared light-driven single atom photocatalyst enables spontaneous dinitrogen reduction to ammonia. Nano Lett 19:6391–6399. https://doi.org/10.1021/acs.nanolett.9b02572
Nguyen V-H, Che-Chin Yu J, Huang C-W, Wu JC-S (2020) Recent advances in the development of photocatalytic NOx abatement. Elsevier
Nilsson Pingel T, Jørgensen M, Yankovich AB, Grönbeck H, Olsson E (2018) Influence of atomic site-specific strain on catalytic activity of supported nanoparticles. Nat Commun 9. https://doi.org/10.1038/s41467-018-05055-1
Qiao B, Liang JX, Wang A, Xu CQ, Li J, Zhang T, Liu JJ (2015) Ultrastable single-atom gold catalysts with strong covalent metal-support interaction (CMSI). Nano Res 8:2913–2924. https://doi.org/10.1007/s12274-015-0796-9
Smith AM, Mohs AM, Nie S (2009) Tuning the optical and electronic properties of colloidal nanocrystals by lattice strain. Nat Nanotechnol 4:56–63. https://doi.org/10.1038/nnano.2008.360
Sun T, Xu L, Wang D, Li Y (2019) Metal organic frameworks derived single atom catalysts for electrocatalytic energy conversion. Nano Res 12:2067–2080. https://doi.org/10.1007/s12274-019-2345-4
Takata T, Jiang J, Sakata Y, Nakabayashi M, Shibata N, Nandal V, Seki K, Hisatomi T, Domen K (2020) Photocatalytic water splitting with a quantum efficiency of almost unity. Nature 581:411–414. https://doi.org/10.1038/s41586-020-2278-9
Tao H, Choi C, Ding LX, Jiang Z, Han Z, Jia M, Fan Q, Gao Y, Wang H, Robertson AW, Hong S, Jung Y, Liu S, Sun Z (2019) Nitrogen fixation by Ru single-atom electrocatalytic reduction. Chem 5:204–214. https://doi.org/10.1016/j.chempr.2018.10.007
Tong T, Zhu B, Jiang C, Cheng B, Yu J (2018) Mechanistic insight into the enhanced photocatalytic activity of single-atom Pt, Pd or Au-embedded g-C 3 N 4. Elsevier B.V
Wang A, Li J, Zhang T (2018) Heterogeneous single-atom catalysis. Nat Rev Chem 2:65–81. https://doi.org/10.1038/s41570-018-0010-1
Wang B, Cai H, Shen S (2019a) Single metal atom photocatalysis. Small Methods 3:1–14. https://doi.org/10.1002/smtd.201800447
Wang Q, Zhang D, Chen Y, Fu WF, Lv XJ (2019b) Single-atom catalysts for photocatalytic reactions. ACS Sustain Chem Eng 7:6430–6443. https://doi.org/10.1021/acssuschemeng.8b06273
Wei H, Huang K, Wang D, Zhang R, Ge B, Ma J, Wen B, Zhang S, Li Q, Lei M, Zhang C, Irawan J, Liu LM, Wu H (2017) Iced photochemical reduction to synthesize atomically dispersed metals by suppressing nanocrystal growth. Nat Commun 8:1–8. https://doi.org/10.1038/s41467-017-01521-4
Westsson E, Picken S, Koper G (2019) The effect of lattice strain on catalytic activity. Chem Commun 55:1338–1341. https://doi.org/10.1039/c8cc09063g
Xing J, Chen JF, Li YH, Yuan WT, Zhou Y, Zheng LR, Wang HF, Hu P, Wang Y, Zhao HJ, Wang Y, Yang HG (2014) Stable isolated metal atoms as active sites for photocatalytic hydrogen evolution. Chem A Eur J 20:2138–2144. https://doi.org/10.1002/chem.201303366
Xu T, Zheng H, Zhang P (2020) Isolated Pt single atomic sites anchored on nanoporous TiO2 film for highly efficient photocatalytic degradation of low concentration toluene. J Hazard Mater 388. https://doi.org/10.1016/j.jhazmat.2019.121746
Yan H, Cheng H, Yi H, Lin Y, Yao T, Wang C, Li J, Wei S, Lu J, Yan H, Cheng H, Yi H, Lin Y, Yao T, Wang C, Li J, Wei S (2015) Single-atom Pd1/graphene catalyst achieved by atomic layer deposition: remarkable performance in selective hydrogenation of 1, 3-butadiene. J Am Chem Soc 137:10484–10487
Yang Y, Zeng G, Huang D, Zhang C, He D, Zhou C, Wang W, Xiong W, Song B, Yi H, Ye S, Ren X (2020) In situ grown single-atom cobalt on polymeric carbon nitride with bidentate ligand for efficient photocatalytic degradation of refractory antibiotics. Small 16:1–12. https://doi.org/10.1002/smll.202001634
Zeng L, Xue C (2020) Single metal atom decorated photocatalysts: progress and challenges. Nano Res 12. https://doi.org/10.1007/s12274-020-3099-8
Zeng L, Dai C, Liu B, Xue C (2019) Oxygen-assisted stabilization of single-atom Au during photocatalytic hydrogen evolution. J Mater Chem A 7:24217–24221. https://doi.org/10.1039/c9ta10290f
Zeng Z, Su Y, Quan X, Choi W, Zhang G, Liu N, Kim B, Chen S, Yu H, Zhang S (2020) Single-atom platinum confined by the interlayer nanospace of carbon nitride for efficient photocatalytic hydrogen evolution. Nano Energy 69:104409. https://doi.org/10.1016/j.nanoen.2019.104409
Zhang L, Ren Y, Liu W, Wang A, Zhang T (2018a) Single-atom catalyst: a rising star for green synthesis of fine chemicals. Natl Sci Rev 5:653–672. https://doi.org/10.1093/nsr/nwy077
Zhang H, Liu G, Shi L, Ye J (2018b) Single-atom catalysts: emerging multifunctional materials in heterogeneous catalysis. Adv Energy Mater 8:1–24. https://doi.org/10.1002/aenm.201701343
Zhou Y, Doronkin DE, Zhao Z, Plessow PN, Jelic J, Detlefs B, Pruessmann T, Studt F, Grunwaldt JD (2018) Photothermal catalysis over nonplasmonic Pt/TiO2 studied by operando HERFD-XANES, resonant XES, and DRIFTS. ACS Catal 8:11398–11406. https://doi.org/10.1021/acscatal.8b03724
Zhou P, Lv F, Li N, Zhang Y, Mu Z, Tang Y, Lai J, Chao Y, Luo M, Lin F, Zhou J, Su D, Guo S (2019) Strengthening reactive metal-support interaction to stabilize high-density Pt single atoms on electron-deficient g-C3N4 for boosting photocatalytic H2 production. Nano Energy 56:127–137. https://doi.org/10.1016/j.nanoen.2018.11.033
Zhou L, Martirez JMP, Finzel J, Zhang C, Swearer DF, Tian S, Robatjazi H, Lou M, Dong L, Henderson L, Christopher P, Carter EA, Nordlander P, Halas NJ (2020a) Light-driven methane dry reforming with single atomic site antenna-reactor plasmonic photocatalysts. Nat Energy 5:61–70. https://doi.org/10.1038/s41560-019-0517-9
Zhou X, Chen L, Sterbinsky GE, Mukherjee D, Unocic RR, Tait SL (2020b) Pt-Ligand single-atom catalysts: tuning activity by oxide support defect density. Cat Sci Technol 10:3353–3365. https://doi.org/10.1039/c9cy02594d
Zuo Q, Liu T, Chen C, Ji Y, Gong X, Mai Y, Zhou Y (2019) Ultrathin metal–organic framework nanosheets with ultrahigh loading of single Pt atoms for efficient visible-light-driven photocatalytic H2 evolution. Angew Chem Int Ed 58:10198–10203. https://doi.org/10.1002/anie.201904058
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2022 The Author(s), under exclusive license to Springer Nature Switzerland AG
About this entry
Cite this entry
Khandelwal, A., Maarisetty, D., Baral, S.S. (2022). Single-Atom Photocatalysts for Energy and Environmental Sustainability. In: Hussain, C.M., Di Sia, P. (eds) Handbook of Smart Materials, Technologies, and Devices. Springer, Cham. https://doi.org/10.1007/978-3-030-84205-5_85
Download citation
DOI: https://doi.org/10.1007/978-3-030-84205-5_85
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-030-84204-8
Online ISBN: 978-3-030-84205-5
eBook Packages: EngineeringReference Module Computer Science and Engineering