Bottom-up evolution of perovskite clusters into high-activity rhodium nanoparticles toward alkaline hydrogen evolution

Gaoxin Lin^#^{1

2}, Zhuang Zhang^#^{1

2}, Qiangjian Ju^#^{1

2}, Tong Wu^{1

2}, Carlo U Segre³, Wei Chen⁴, Hongru Peng⁵, Hui Zhang⁶, Qiunan Liu⁷, Zhi Liu^{5

6}, Yifan Zhang^{1

2}, Shuyi Kong^{1

2}, Yuanlv Mao^{1

2}, Wei Zhao^{1

2}, Kazu Suenaga⁷, Fuqiang Huang^{8

9}, Jiacheng Wang^{10

11

12

13}

Affiliations

¹ State Key Lab of High Performance Ceramics and Superfine microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 201899, Shanghai, China.
² Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, 100049, Beijing, China.
³ Department of Physics & Center for Synchrotron Radiation Research and Instrumentation, Illinois Institute of Technology, Chicago, IL, 60616, USA.
⁴ Department of Mechanical, Materials and Aerospace Engineering, Illinois Institute of Technology, Chicago, IL, 60616, USA.
⁵ School of Physical Science and Technology, ShanghaiTech University, 201210, Shanghai, China.
⁶ State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, 200050, Shanghai, China.
⁷ SANKEN, Osaka University, Ibaraki, 567-0047, Japan.
⁸ State Key Lab of High Performance Ceramics and Superfine microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 201899, Shanghai, China. huangfq@mail.sic.ac.cn.
⁹ State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, 100871, Beijing, China. huangfq@mail.sic.ac.cn.
¹⁰ State Key Lab of High Performance Ceramics and Superfine microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 201899, Shanghai, China. jiacheng.wang@mail.sic.ac.cn.
¹¹ Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, 100049, Beijing, China. jiacheng.wang@mail.sic.ac.cn.
¹² Hebei Provincial Key Laboratory of Inorganic Nonmetallic Materials, College of Materials Science and Engineering, North China University of Science and Technology, 063210, Tangshan, China. jiacheng.wang@mail.sic.ac.cn.
¹³ School of Materials Science and Engineering, Taizhou University, 318000, Taizhou, Zhejiang, China. jiacheng.wang@mail.sic.ac.cn.

^# Contributed equally.

PMID: 36650135
PMCID: PMC9845238
DOI: 10.1038/s41467-023-35783-y

Bottom-up evolution of perovskite clusters into high-activity rhodium nanoparticles toward alkaline hydrogen evolution

Gaoxin Lin et al. Nat Commun. 2023.

. 2023 Jan 17;14(1):280.

doi: 10.1038/s41467-023-35783-y.

Authors

Affiliations

¹ State Key Lab of High Performance Ceramics and Superfine microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 201899, Shanghai, China.
² Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, 100049, Beijing, China.
³ Department of Physics & Center for Synchrotron Radiation Research and Instrumentation, Illinois Institute of Technology, Chicago, IL, 60616, USA.
⁴ Department of Mechanical, Materials and Aerospace Engineering, Illinois Institute of Technology, Chicago, IL, 60616, USA.
⁵ School of Physical Science and Technology, ShanghaiTech University, 201210, Shanghai, China.
⁶ State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, 200050, Shanghai, China.
⁷ SANKEN, Osaka University, Ibaraki, 567-0047, Japan.
⁸ State Key Lab of High Performance Ceramics and Superfine microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 201899, Shanghai, China. huangfq@mail.sic.ac.cn.
⁹ State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, 100871, Beijing, China. huangfq@mail.sic.ac.cn.
¹⁰ State Key Lab of High Performance Ceramics and Superfine microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 201899, Shanghai, China. jiacheng.wang@mail.sic.ac.cn.
¹¹ Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, 100049, Beijing, China. jiacheng.wang@mail.sic.ac.cn.
¹² Hebei Provincial Key Laboratory of Inorganic Nonmetallic Materials, College of Materials Science and Engineering, North China University of Science and Technology, 063210, Tangshan, China. jiacheng.wang@mail.sic.ac.cn.
¹³ School of Materials Science and Engineering, Taizhou University, 318000, Taizhou, Zhejiang, China. jiacheng.wang@mail.sic.ac.cn.

^# Contributed equally.

PMID: 36650135
PMCID: PMC9845238
DOI: 10.1038/s41467-023-35783-y

Abstract

Self-reconstruction has been considered an efficient means to prepare efficient electrocatalysts in various energy transformation process for bond activation and breaking. However, developing nano-sized electrocatalysts through complete in-situ reconstruction with improved activity remains challenging. Herein, we report a bottom-up evolution route of electrochemically reducing Cs₃Rh₂I₉ halide-perovskite clusters on N-doped carbon to prepare ultrafine Rh nanoparticles (~2.2 nm) with large lattice spacings and grain boundaries. Various in-situ and ex-situ characterizations including electrochemical quartz crystal microbalance experiments elucidate the Cs and I extraction and Rh reduction during the electrochemical reduction. These Rh nanoparticles from Cs₃Rh₂I₉ clusters show significantly enhanced mass and area activity toward hydrogen evolution reaction in both alkaline and chlor-alkali electrolyte, superior to liquid-reduced Rh nanoparticles as well as bulk Cs₃Rh₂I₉-derived Rh via top-down electro-reduction transformation. Theoretical calculations demonstrate water activation could be boosted on Cs₃Rh₂I₉ clusters-derived Rh nanoparticles enriched with multiply sites, thus smoothing alkaline hydrogen evolution.

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Conflict of interest statement

The authors declare no competing interests.

Figures

Fig. 1. Schematic illustration of synthesizing perovskite Cs₃Rh₂I₉ bulk crystals and clusters Cs₃Rh₂I₉/NC, and their electrochemical reduction into metallic Rh particles toward alkaline HER.
a Synthesis of Cs₃Rh₂I₉ bulk crystal via a solid reaction using I₂, Rh, and CsI at 800 ^oC. The Cs₃Rh₂I₉ crystal could demonstrate a dissolution-precipitation phenomenon in N, N-dimethylformamide (DMF). b Electrochemical reduction of Cs₃Rh₂I₉ clusters (~1.7 nm) supported on NC (Cs₃Rh₂I₉/NC) to form Cs₃Rh₂I₉/NC-R with a little larger size (~2.2 nm) via a bottom-up evolution route. c Electrochemical reduction of bulk Cs₃Rh₂I₉ to form Cs₃Rh₂I₉-R with vert large particle size via a top-down route. d Liquid reduction of RhCl₃ in aqueous to form Rh/NC with average particle size of 2.4 nm as the control catalyst. e HER polarization curves of Cs₃Rh₂I₉/NC-R, Cs₃Rh₂I₉-R, and Rh/NC coated on rotating glassy carbon electrode (GCE, 1600 rpm) in a chlorine-alkali electrolyte. f HER mass activity comparison in a chlorine-alkali electrolyte for Cs₃Rh₂I₉/NC-R, Cs₃Rh₂I₉-R, and Rh/NC electrocatalysts at an overpotential of 50 mV.

**Fig. 2. Structure characterization of bulk Cs₃Rh₂I₉ and nanoclusters Cs₃Rh₂I₉/NC.**
a Atomic structure, and (b) powder XRD pattern and simulated pattern of Cs₃Rh₂I₉ crystal. c Diffuse-reflectance UV–Vis spectrum of Cs₃Rh₂I₉. The inset shows the corresponding Tauc plot. d SEM-EDX mapping images of Cs₃Rh₂I₉ single crystal. e HAADF-STEM image of Cs₃Rh₂I₉ crystal. f TEM image of Cs₃Rh₂I₉ clusters supported on NC (Cs₃Rh₂I₉/NC, Rh content: 5.8 wt.%). The insets show the corresponding HAADF image (scale bar: 5 nm, up) and particle size distribution (down). g TEM-EDX mapping of Cs₃Rh₂I₉/NC. h XPS spectra of Rh 3d for Cs₃Rh₂I₉ and Cs₃Rh₂I₉/NC. i Fourier transform EXAFS of Rh K-edge in R-space for Cs₃Rh₂I₉, Cs₃Rh₂I₉/NC, and Rh foil.

**Fig. 3. Reconstruction of clusters Cs₃Rh₂I₉/NC into Rh nanoparticles on NC.**
a The CV curves from 1^st to 100^th cycle at 100 mV s⁻¹ for Cs₃Rh₂I₉/NC in 1.0 M KOH. b Mass change of the Cs₃Rh₂I₉/NC electrode monitored by in situ EQCM experiment. c ICP-MS of the Cs and Rh contents in the electrolyte at different reduction time. d XPS spectra of Rh 3d for Cs₃Rh₂I₉/NC at different reduction time. The results in (b–d) were obtained at the potentiostatic measurement at −0.03 V vs. RHE.

**Fig. 4. Characterization of Cs₃Rh₂I₉/NC-R prepared by electrochemical reduction of Cs₃Rh₂I₉/NC.**
a TEM image of Cs₃Rh₂I₉/NC-R, showing uniform dispersion of Rh nanoparticles. The inset shows the corresponding HAADF image (scale bar: 5 nm, up) and particle size distribution (down). b The linear electron energy loss spectroscopy of Cs₃Rh₂I₉/NC-R. c Fourier transform EXAFS of the Rh K-edge in R-space for Cs₃Rh₂I₉/NC, Cs₃Rh₂I₉/NC-R and Rh foil. d WT-EXAFS images of Rh for Cs₃Rh₂I₉/NC, Cs₃Rh₂I₉/NC-R and Rh foil. e HAADF-STEM image of Cs₃Rh₂I₉/NC-R, showing a single Rh nanoparticle with larger lattice spacing and twin-GBs. f HRTEM image of Rh nanoparticles (Cs₃Rh₂I₉-R) derived from the top-down electrochemical reduction of bulk Cs₃Rh₂I₉ crystal. g DFT models of Rh with larger lattice spacing and GBs (up panel) and Rh with regular lattice spacing (down panel).

**Fig. 5. HER activity in 1.0 M KOH and chlor-alkali electrolyte.**
a LSV curves of various electrocatalysts including commercial Pt/C (Pt content: 20 wt.%) coated on rotating glassy carbon electrode (GCE, 1600 rpm) in 1.0 M KOH. The catalyst loading amount on GCE is 0.764 mg cm⁻². For Rh-based samples, the calculated Rh loading amounts on GCE are 0.045, 0.090 and 0.053 mg cm⁻² for Cs₃Rh₂I₉/NC-R, Cs₃Rh₂I₉-R, and Rh/NC, respectively. b Comparison of overpotential at 10 mA cm⁻² and Tafel slope for various Rh-based catalysts in 1.0 M KOH. c LSV curves of various electrocatalysts coated on rotating GCE (1600 rpm) in chlorine-alkali electrolyte. d Mass activity normalized to the mass of Rh in chlorine-alkali electrolyte. e Comparison of mass activity and area activity at the overpotential of 50 mV in chlorine-alkali electrolyte. All data show the mean and standard deviation through three repeated measurements. f Stability of Cs₃Rh₂I₉/NC-R at 10 mA cm⁻² in a chlorine-alkali electrolyte.

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Bottom-up evolution of perovskite clusters into high-activity rhodium nanoparticles toward alkaline hydrogen evolution

Affiliations

Bottom-up evolution of perovskite clusters into high-activity rhodium nanoparticles toward alkaline hydrogen evolution

Authors

Affiliations

Abstract

Conflict of interest statement

Figures

References

Grants and funding

LinkOut - more resources

Full Text Sources