Noble Metal Phosphide Electrocatalysts and Their Synchrotron-based X-ray Absorption Spectroscopy

doi:10.15541/jim20200224

Abstract

Abstract:

Electrocatalytic technology is one of the most attractive technologies for renewable energy storage and conversion, and nano-scale noble metals exhibit excellent electrocatalytic activity. However, because of the scarcity of precious metal resources and high development costs, reducing the dosage of precious metals while improving activity and durability of catalysts is always the research focus in the field of catalysis applications. Among various candidates, noble metal phosphide-based new electrocatalysts have received widespread attention due to their multifunctional active sites, adjustable structure and composition, and unique physical and chemical properties. Compared with transition metal phosphide, noble metal phosphides have higher intrinsic activity, and exhibit better stability under acid condition. In this review, the research progress of noble metal phosphides was mainly summarized including design synthesis, structural engineer, X-ray absorption spectroscopic characterization, and electrocatalytic applications. Eventually, the current challenges and opportunities for the development of noble metal phosphide-based electrocatalysts were discussed, along with the future prospection of in situ synchrotron radiation X-ray characterizations that might be applied in this field.

Key words: noble metal phosphide, electrocatalysis, synchrotron radiation, X-ray absorption spectroscopy, review

CLC Number:

TQ174

ZHOU Yuzhu, ZHANG Youkui, SONG Li. Noble Metal Phosphide Electrocatalysts and Their Synchrotron-based X-ray Absorption Spectroscopy[J]. Journal of Inorganic Materials, 2021, 36(3): 225-244.

Figures/Tables 15

Fig. 1 The structures of selected platinum group metal (PGM) phosphides. The metal atoms displayed in grey and the phosphorus atoms displayed in red[11] (a) Rh2P crystallizes in the anti-CaF2 structure; (b) Rh2P3; (c) Rh4P3; (d) RhP2 crystallizes in the CoSb2 structure forming P2 dimers; (e) RhP3 crystallizes in the CoAs3 structure forming Rh4-4 rings; (f) Co2P structure with chains of slightly distorted prisms

Fig. 2 Schematic illustration of the synthetic process for Ru-u2P/PC (a)[40] and RhP/rGO (b)[15]

Fig. 3 General synthesis procedure of MPx@NPGC and corresponding XRD patterns (a)[45], schematic illustration of preparation for Ru2P@PNC/CC-900 (b)[53]

Fig. 4 TEM (a) and HRTEM (b) images of single Rh-P particle of Rh-P/CP, STEM and elemental mapping images for single Rh-P particle Rh (c) and P (d)[56], synthesis diagram of Ru-Ru2PΦNPC and NPC@RuO2 (e)[59]

Fig. 5 XRD patterns for RhPx@NPC and XPS spectra for the Rh3d and P2p regions of RhPx@NPC catalysts (a)[65], Partial density of states (PDOS) projected on the d orbitals of Rh atoms at the surfaces of Rh(111), Rh2P(200) and RhP2(ˉ111) (b) (The red dash and yellow solid lines indicate the Fermi level (EF) and the location of d-bands center, respectively), electrocatalytic activities of Pt/C, Rh NS/C, and w-Rh2P NS/C in 0.1 mol/L KOH (c), free energy pathways (?G) for HER of P-terminated (PT-Rh2P (200)), Rh-terminated (RhT-Rh2P (200)), and Rh (100) surfaces, respectively, under alkaline condition (d)[71]

Fig. 6 XPS results (a, b): Ir4f for IrP2/NPC before and after the OER/HER tests[32], schematic of the HER processes by RuxPNFs under alkaline conditions (c)[75], TEM, HR-TEM images of PdP2@CB before durability test in 1 mol/L KOH electrolyte (d) after durability test in 1 mol/L KOH electrolyte (e), and HER performance (f) of PdP2@CB in 0.5 mol/L H2SO4[69]

Fig. 7 Schematic illustration of the synthesis and structure of the RuPx/NPG electrocatalyst (a)[77], TEM images of NC, NPC, Rh@NC, and RhPx@NPC nanoshells (b)[78], schematic illustration of the synthesis and structure of Rh2P@NPC and RhP2@NPC (c)[65], TEM image and EDS elemental mapping of Rh, P, C and N for RhP2@NPC (d), and SEM image of the PtNiP MNs (e)[73]

Fig. 8 XRD patterns of RuPx synthesized in different temperatures (a)[44], theoretical models used in DFT calculations and adopted adsorption sites of H* on the surface of these models, calculated free-energy diagram of HER at equilibrium potential for Ru2P, RuP, and RuP2 (b)[46], the calculated water dissociation barrier and water dissociation pathway for RuP (121) and RuP2 (101) surfaces (c)[54]

Fig. 9 HRTEM (a) and FFT (b) images of Ru-Ru2PΦNPC, HER performance of Ru-Ru2PΦNPC, Ru/C, Ru2P/C, NPC, and 20wt% Pt/C, ?GH* calculated at the equilibrium potential of different models (c)[59], high-resolution HAADF-STEM(d) and HR-TEM (f) images of a Ru-Ru2P nanoparticle, pH dependences of the Tafel slopes of the Ru-Ru2P/PC and Pt/C catalysts, cyclic stability of the Ru-Ru2P/PC (f)[40], schematic illustration of a formation process for the hollow Ru-RuxP-CoxP polyhedra (g), Gibbs free energy diagram for the OER at different potentials on the surface of Co2P and Ru-RuPx-CoxP models (h)[85]

Fig. 10 Pt4f core level of BPed Pt/GR with different amounts of BP (a), chemical state contents of the PtNPs as a function of BP adding amount (b), free energy diagram for HER with different Pt-P contents with ΔGH* in each system (c)[88], proposed photocatalytic mechanism of 0.1%-RP/g-CN for H2 evolution (d)[89], kinetics curves of H2 production over Pt/g-C3N4 and RhPx/g-C3N4-5%, cyclic running kinetics curves of H2 production over RhPx/g-C3N4-5% (e1-e2)[90]

Fig. 11 TEM (a,b), and HRTEM (c) images of Rh2P@NC, polarization curves for Rh2P@NC (initial and after 1000 CV scanning) and time-dependent current density curve for Rh2P@NC under static overpotential of 20 mV for 10 h (d)[51], electrocatalytic properties for the HER in 1.0 mol/L KOH of Ru2P/RGO-20, Ru2P and Pt/C (e), free-energy diagram of the HER for RGO, Ru2P, Pt and Ru2P/RGO-20 (f)[81], band structure of pure RuP2 (left) and RuP2@NPC hybrid (right) (g)[93], HER polarization curves of the pure metal phosphides and the physical mixture of different metal phosphides and graphene in 0.5 mol/L H2SO4 and 1 mol/L KOH (h)[45]

Fig. 12 Schematic illustration of the fabrication of Ru-MnFeP/NF catalysts (a), calculated charge density differences of Fe2P-Ru and Mn2P-Ru structures (b)[98], high-resolution XPS spectra of Ni2p, Fe2p and P2p in the Ru-NiFe-P and the NiFe-P (c), the absorption modeled surfaces of Ru-NiFe-P (d), calculated ΔGH* for Ru-NiFe-P, NiFe-P, Ru-Ni-P, Ni-P, Ru-Fe-P and Fe-P (e), total density of states of Ru-NiFe-P and NiFe-P (f)[99]

Fig. 13 HRTEM image of PdNP-CN (a), HAADF-STEM images of PdPNP-CN (b) and PdPSA-CN (c), the geometry structures of PdNP-CN (d), PdPNP-CN (e) and PdPSA-CN (f), Pd K-edge XANES spectra (g) and the corresponding k3-weighted FT spectra at R(h) and k(i) space[ 103], EXAFS spectra (j) of RuCl3@HPN and Ru SAs@PN, Wavelet transform (k) of Ru SAs@PN, Ru foil and RuCl3@HPN samples, N K edge (l) and P L edge (m) NEXAFS spectra, 31P solid state MAS NMR spectra at room temperature using a direct acquisition with proton decoupling of PN and RuβSAs@PN (n)[104] (1 ?=10 nm)

Fig. 14 In situ silver K-edge XANES (a) and EXAFS spectra (b) of AgP2 NCs, AgO, Ag2O, and Ag foil, Faradaic efficiency of the CO and CO:H2 ratio as a function of Agδ+ in AgP2 and Ag (c), linear combination of AgO, Ag2O, and Ag spectra (solid line) compared to the raw Ag K-edge (d), Ag K-edge XANES spectra of AgP2 NCs with respect to CRR time under a constant applied potential of -0.8 V (vs. RHE) (e), Ag K-edge spectra of AgO and Ag2O references before and after CRR at -0.8 V (vs. RHE) for 50 s (f)[38]

Fig. 15 Schematic illustration of the formation of Ni@Ni2P-Ru HNRs (a), Ni K-edge XANES spectra (b) and Fourier transformed k3-weighted EXAFS spectra of Ni@Ni2P-Ru, Ni@Ni2P, and reference Ni foil (c), Ru K-edge XANES spectra of Ni@Ni2P-Ru and reference Ru foil (d), dependence of the Ru(0) and Ru(IV) atomic fractions of the Ni@Ni2P-Ru HNRs as a function of photon energy (e)[108], Ni2p XPS comparison (f) and Ni L edge XANES comparison between Ni5P4-Ru and Ni5P4 (g), XANES (h) and EXAFS (i) results of Ni5P4-Ru, Ni5P4, Ni foil, and NiO at Ni K edge, respectively, Ru K-edge XAFS spectra (j) and the Ru K-edge k2-weighted EXAFS profiles of Ru foil, Ni5P4-Ru, and RuO2 (k)[97]

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