1.
2.
3.
4.
Ligand exchange of PtSA@CdSe with CdBr2 and MUA. MUA
(232 mg) and KOH (236 mg) were dissolved in H2O (4.38 mL). A toluene
dispersion of PtSA@CdSe (3 mM of Se, 1000 µL) was centrifuged. The
sediment was rinsed with a toluene/anhydrous MeCN/DMSO
(45:45:10) solution of CdBr2·4H2O (60 mM, 1000 µL) three times and
with toluene/anhydrous MeCN (1:1, 1000 µL) twice by redispersion and
centrifugation. The sediment was dispersed in the aqueous solution of
MUA and KOH (1000 µL). The dispersion was stirred at 20 °C for 1 h.
The solids were collected by centrifugation and rinsed with MeOH
(1000 µL) twice by redispersion and centrifugation. The sediment was
redispersed in H2O (1000 µL) and subjected to dispersion-state analyses and photocatalysis. For powder-state analyses, the solids were
Nature Communications | (2023)14:4241
5.
6.
7.
8.
Qiao, B. et al. Single-atom catalysis of CO oxidation using Pt1/FeOx.
Nat. Chem. 3, 634–641 (2011).
Xi, J. et al. Synthesis strategies, catalytic applications, and performance regulation of single‐atom catalysts. Adv. Funct. Mater. 31,
2008318 (2021).
Datye, A. K. & Guo, H. Single atom catalysis poised to transition from
an academic curiosity to an industrially relevant technology. Nat.
Commun. 12, 895 (2021).
Xia, J. et al. Construction of single-atom catalysts for electro-,
photo- and photoelectro-catalytic applications: state-of-the-art,
opportunities, and challenges. Mater. Today 53, 217–237 (2022).
Hannagan, R. T., Giannakakis, G., Flytzani-Stephanopoulos, M. &
Sykes, E. C. H. Single-atom alloy catalysis. Chem. Rev. 120,
12044–12088 (2020).
Huo, J. et al. Macro/micro-environment regulating carbonsupported single-atom catalysts for hydrogen/oxygen conversion
reactions. Small 18, e2202394 (2022).
Zhang, W., Fu, Q., Luo, Q., Sheng, L. & Yang, J. Understanding
single-atom catalysis in view of theory. JACS Au 1, 2130–2145 (2021).
Xia, Y., Sayed, M., Zhang, L., Cheng, B. & Yu, J. Single-atom heterogeneous photocatalysts. Chem. Catal. 1, 1173–1214 (2021).
10
Article
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
Ji, S. et al. Chemical synthesis of single atomic site catalysts. Chem.
Rev. 120, 11900–11955 (2020).
Zhang, Z. et al. Coordination structure at work: atomically dispersed
heterogeneous catalysts. Coord. Chem. Rev. 460, 214469
(2022).
Yang, M. et al. Catalytically active Au-O(OH)x-species stabilized by
alkali ions on zeolites and mesoporous oxides. Science 346,
1498–1501 (2014).
Cao, L. et al. Atomically dispersed iron hydroxide anchored on Pt for
preferential oxidation of CO in H2. Nature 565, 631–635 (2019).
Sun, L., Han, L., Huang, J., Luo, X. & Li, X. Single-atom catalysts for
photocatalytic hydrogen evolution: a review. Int. J. Hydrog. Energy
47, 17583–17599 (2022).
Shi, Y. et al. Electronic metal-support interaction modulates singleatom platinum catalysis for hydrogen evolution reaction. Nat.
Commun. 12, 3021 (2021).
Shi, Y. et al. Energy level engineering of MoS2 by transition-metal
doping for accelerating hydrogen evolution reaction. J. Am. Chem.
Soc. 139, 15479–15485 (2017).
Zhou, P. et al. Single-atom Pt-I3 sites on all-inorganic Cs2SnI6 perovskite for efficient photocatalytic hydrogen production. Nat.
Commun. 12, 4412 (2021).
Wu, X. et al. Engineering the coordination sphere of isolated active
sites to explore the intrinsic activity in single-atom catalysts. NanoMicro Lett. 13, 136 (2021).
Zhang, Y. et al. The effect of coordination environment on the
activity and selectivity of single-atom catalysts. Coord. Chem. Rev.
461, 214493 (2022).
Liu, D., He, Q., Ding, S. & Song, L. Structural regulation and support
coupling effect of single‐atom catalysts for heterogeneous catalysis. Adv. Energy Mater. 10, 2001482 (2020).
Li, X., Rong, H., Zhang, J., Wang, D. & Li, Y. Modulating the local
coordination environment of single-atom catalysts for enhanced
catalytic performance. Nano Res. 13, 1842–1855 (2020).
Liu, J.-C., Tang, Y., Wang, Y.-G., Zhang, T. & Li, J. Theoretical
understanding of the stability of single-atom catalysts. Natl Sci. Rev.
5, 638–641 (2018).
Wang, X. et al. Single-atom engineering to ignite 2D transition metal
dichalcogenide based catalysis: fundamentals, progress, and
beyond. Chem. Rev. 122, 1273–1348 (2022).
Shi, Y. et al. Site-specific electrodeposition enables self-terminating
growth of atomically dispersed metal catalysts. Nat. Commun. 11,
4558 (2020).
Shi, X. et al. Protruding Pt single-sites on hexagonal ZnIn2S4 to
accelerate photocatalytic hydrogen evolution. Nat. Commun. 13,
1287 (2022).
Lan, S. et al. Protrudent iron single-atom accelerated interfacial
piezoelectric polarization for self-powered water motion triggered
Fenton-like reaction. Small 18, e2105279 (2022).
Zhang, Z. et al. Selectively anchoring single atoms on specific sites
of supports for improved oxygen evolution. Nat. Commun. 13,
2473 (2022).
Shen, R. et al. High-concentration single atomic Pt sites on hollow
CuSx for selective O2 reduction to H2O2 in acid solution. Chem 5,
2099–2110 (2019).
Luo, Y. X., Qiu, W. B., Liang, R. P., Xia, X. H. & Qiu, J. D. Mo-doped FeP
nanospheres for artificial nitrogen fixation. ACS Appl. Mater. Interfaces 12, 17452–17458 (2020).
Jiang, K. et al. Single platinum atoms embedded in nanoporous
cobalt selenide as electrocatalyst for accelerating hydrogen evolution reaction. Nat. Commun. 10, 1743 (2019).
Li, H. et al. Synergetic interaction between neighbouring platinum
monomers in CO2 hydrogenation. Nat. Nanotechnol. 13, 411–417
(2018).
Nature Communications | (2023)14:4241
https://doi.org/10.1038/s41467-023-40003-8
31. Deng, J. et al. Triggering the electrocatalytic hydrogen evolution
activity of the inert two-dimensional MoS2 surface via single-atom
metal doping. Energy Environ. Sci. 8, 1594–1601 (2015).
32. Son, J. S. et al. Large-scale soft colloidal template synthesis of 1.4
nm thick CdSe nanosheets. Angew. Chem. Int. Ed. 48,
6861–6864 (2009).
33. Pang, Y. et al. Why do colloidal wurtzite semiconductor nanoplatelets have an atomically uniform thickness of eight monolayers? J.
Phys. Chem. Lett. 10, 3465–3471 (2019).
34. Sun, H. & Buhro, W. E. Contrasting ligand-exchange behavior of
wurtzite and zinc-blende cadmium telluride nanoplatelets. Chem.
Mater. 33, 1683–1697 (2021).
35. Zhou, Y., Wang, F. & Buhro, W. E. Large exciton energy shifts by
reversible surface exchange in 2D II-VI nanocrystals. J. Am. Chem.
Soc. 137, 15198–15208 (2015).
36. Ji, C. & Buhro, W. E. Two-phase ligand exchanges on CdSe nanoplatelets. Chem. Mater. 32, 5290–5300 (2020).
37. Yao, Y., Zhou, Y., Sanderson, W. M., Loomis, R. A. & Buhro, W. E.
Metal-halide-ligated cadmium selenide quantum belts by facile
surface exchange. Chem. Mater. 30, 2848–2857 (2018).
38. Melanson, R. & Rochon, F. D. The crystal structure of cis-dichlorobis(dimethylsulfoxide)platinum(II). Can. J. Chem. 53, 2371–2374
(1975).
39. Wu, X. et al. Surface step decoration of isolated atom as electron
pumping: atomic-level insights into visible-light hydrogen evolution. Nano Energy 45, 109–117 (2018).
40. Li, J. et al. Thermal phase control of two-dimensional Pt-chalcogenide (Se and Te) ultrathin epitaxial films and nanocrystals. Chem.
Mater. 33, 8018–8027 (2021).
41. De Trizio, L. & Manna, L. Forging colloidal nanostructures via cation
exchange reactions. Chem. Rev. 116, 10852–10887 (2016).
42. Kawasaki, S. et al. Epitaxial Rh-doped SrTiO3 thin film photocathode
for water splitting under visible light irradiation. Appl. Phys. Lett.
101, 033910 (2012).
43. Wright, J. T., Forsythe, K., Hutchins, J. & Meulenberg, R. W. Implications of orbital hybridization on the electronic properties of
doped quantum dots: the case of Cu:CdSe. Nanoscale 8,
9417–9424 (2016).
44. Meulenberg, R. W. et al. Structure and composition of Cu-doped
CdSe nanocrystals using soft X-ray absorption spectroscopy. Nano
Lett. 4, 2277–2285 (2004).
45. Bouet, C. et al. Flat colloidal semiconductor nanoplatelets. Chem.
Mater. 25, 1262–1271 (2013).
46. Wang, F. et al. Two-dimensional semiconductor nanocrystals:
properties, templated formation, and magic-size nanocluster
intermediates. Acc. Chem. Res. 48, 13–21 (2015).
47. Zhang, J., Sun, Y., Ye, S., Song, J. & Qu, J. Heterostructures in twodimensional CdSe nanoplatelets: synthesis, optical properties, and
applications. Chem. Mater. 32, 9490–9507 (2020).
48. Naskar, S. et al. Synthesis of ternary and quaternary Au and Pt
decorated CdSe/CdS heteronanoplatelets with controllable morphology. Adv. Funct. Mater. 27, 1604685 (2017).
49. Li, Q. & Lian, T. Exciton dissociation dynamics and light-driven H2
generation in colloidal 2D cadmium chalcogenide nanoplatelet
heterostructures. Nano Res. 11, 3031–3049 (2018).
50. Li, Q. et al. Two-dimensional morphology enhances light-driven H2
generation efficiency in CdS nanoplatelet-Pt heterostructures. J.
Am. Chem. Soc. 140, 11726–11734 (2018).
51. Kodanek, T. et al. Phase transfer of 1- and 2-dimensional Cd-based
nanocrystals. Nanoscale 7, 19300–19309 (2015).
52. Yao, Y. & Buhro, W. E. Thiol versus thiolate ligation on cadmium
selenide quantum belts. Chem. Mater. 32, 205–214 (2019).
53. Wang, Y., Wang, H., Li, Y., Zhang, M. & Zheng, Y. Designing a 0d/1d
s-scheme heterojunction of cadmium selenide and polymeric
11
Article
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
carbon nitride for photocatalytic water splitting and carbon dioxide
reduction. Molecules 27, 6286 (2022).
Pellegrin, Y. & Odobel, F. Sacrificial electron donor reagents for
solar fuel production. C. R. Chim. 20, 283–295 (2017).
Jiang, K. et al. Rational strain engineering of single-atom ruthenium
on nanoporous MoS2 for highly efficient hydrogen evolution. Nat.
Commun. 12, 1687 (2021).
Qin, Y. et al. Single-atom-based heterojunction coupling with ionexchange reaction for sensitive photoelectrochemical immunoassay. Nano Lett. 21, 1879–1887 (2021).
Sharma, M. et al. Near-unity emitting copper-doped colloidal
semiconductor quantum wells for luminescent solar concentrators.
Adv. Mater. 29, 1700821 (2017).
Hu, H. et al. Construction of single-atom platinum catalysts enabled
by CsPbBr3 nanocrystals. ACS Nano 15, 13129–13139 (2021).
Ravel, B. & Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data
analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiat. 12, 537–541 (2005).
Newville, M., Livins, P., Yacoby, Y., Rehr, J. J. & Stern, E. A. Near-edge
x-ray-absorption fine structure of Pb: a comparison of theory and
experiment. Phys. Rev. B Condens. Matter 47, 14126–14131 (1993).
Zabinsky, S. I., Rehr, J. J., Ankudinov, A., Albers, R. C. & Eller, M. J.
Multiple-scattering calculations of x-ray-absorption spectra. Phys.
Rev. B Condens. Matter 52, 2995–3009 (1995).
Konno, H. & Yamamoto, Y. Ylide–metal complexes. XIII. An X-ray
photoelectron spectroscopic study of bis(dimethylsulfoxonium
methylide)gold chloride. Bull. Chem. Soc. Jpn. 60, 2561–2564
(1987).
Wilson, D. & Langell, M. A. XPS analysis of oleylamine/oleic acid
capped Fe3O4 nanoparticles as a function of temperature. Appl.
Surf. Sci. 303, 6–13 (2014).
Acknowledgements
This research was supported by the Ministry of Education, Culture,
Sports, Science and Technology (MEXT)/Japan Society for the Promotion of Science (JSPS), KAKENHI, for Scientific Research (S) (Grant No.
JP19H05634) and Scientific Research for Innovative Areas (Grant No.
JP16H06520, Coordination Asymmetry) (T.T.). This work was partly
supported by the Japan Science and Technology Agency (JST), CREST
(Grant No. JPMJCR21B4) (T.T.) and FOREST (Grant No. JPMJFR213I) (M.S.).
XAFS measurements were performed at the BL01B1 of SPring-8 with the
approval of the Japan Synchrotron Radiation Research Institute (JASRI)
(Proposal Nos. 2021A1506 and 2021A1380 by Dr R. Takahata and
2021A1319 by Dr K. Matsumoto). Synchrotron XRD measurements were
conducted at the BL02B2 of SPring-8 with the approval of JASRI (Proposal No. 2021B1708 by Dr R. Sato). STEM measurements were conducted at Kyushu University Advanced Characterisation platform within
the framework of the “Nanotechnology Platform” (Proposal No.
JPMXP09A21KU0380 by M.S.). XPS/UPS measurements were conducted at the Japan Advanced Institute of Science and Technology
(JAIST) Molecule and Material Synthesis platform within the framework
Nature Communications | (2023)14:4241
https://doi.org/10.1038/s41467-023-40003-8
of the “Nanotechnology Platform” (Proposal No. S-21-JI-0031 by K.E.).
We thank Dr R. Takahata and Dr K. Matsumoto for their cooperation in
XAFS measurements, Dr R. Sato for conducting synchrotron XRD measurements, Mr M. Kudo for conducting STEM measurements and Mr T.
Murakami for conducting XPS/UPS measurements. We thank Prof. M.
Tosaka and Prof. S. Yamago for providing opportunities for SAXS measurements. We thank Dr Jay Freeman at Edanz (https://jp.edanz.com/ac)
for editing a draft of this manuscript.
Author contributions
K.E. designed this work, performed experiments, analysed the data and
prepared the manuscript. M.S. supervised the research and revised the
manuscript. T.T. supervised the research and revised the manuscript.
Competing interests
The authors declare no competing interests.
Additional information
Supplementary information The online version contains
supplementary material available at
https://doi.org/10.1038/s41467-023-40003-8.
Correspondence and requests for materials should be addressed to
Toshiharu Teranishi.
Peer review information Nature Communications thanks Yongwen Tan,
Wenxian Li, Chuanyi Wang and the other, anonymous, reviewer for their
contribution to the peer review of this work.
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