O-bridged NiSe2/CQDs composite synergistically triggers interfacial electrons transfer to promote H2O2 electrosynthesis

doi:10.1016/S1872-2067(26)65029-2

Abstract

Abstract:

Modulating the electronic structure of electrocatalysts represents a widely employed strategy to enhance the oxygen reduction reaction (ORR) activity and H₂O₂ selectivity, yet achieving precise control over this process remains challenging. In this work, we introduce oxygen-doped carbon quantum dots (O-CQDs) into NiSe₂ nanoparticles/nanosheets to regulate the electronic structure of Ni active sites. This optimization promotes favorable O₂ adsorption and reduces the energy barrier for ^•OOH formation, thereby significantly boosting the electrocatalytic production of H₂O₂ via the two-electron (2e^-) ORR pathway. Combined spectroscopic analysis and density functional theory calculations reveal that the O-bridged interface facilitates electron transfer to surface Ni sites, strengthening O₂ adsorption in an "end-on" configuration and favoring the 2e^- ORR mechanism. The resulting O-bridged NiSe₂/CQDs catalyst exhibits outstanding 2e^- ORR performance under alkaline conditions, achieving a high H₂O₂ production rate of 7458.24 mmol g_cat^-1 h^-1 at 31.25 mA cm^-2 and a Faradaic efficiency of 92.88% at 0.5 V. The efficient degradation of the Rhodamine B and Methylene Blue is achieved by utilizing the electrolyte obtained after the H₂O₂ electrosynthesis process as a Fenton reagent. This study demonstrates that rational tailoring of interfacial charge distribution in hybrid catalysts provides an effective strategy for enhancing catalytic performance, offering a promising design principle for advanced electrocatalysts.

Key words: Two-electron oxygen reduction reaction, Nickel selenides, Oxygen-doped carbon quantum dots, Hydrogen peroxide production, Electronic structure

Qianqian Xu, Haihong Zhong, Chunli Li, Rong Jiang, Yongjun Feng, Luis Alberto Estudillo-Wong. O-bridged NiSe₂/CQDs composite synergistically triggers interfacial electrons transfer to promote H₂O₂ electrosynthesis[J]. Chinese Journal of Catalysis, 2026, 85: 258-271.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65029-2

https://www.cjcatal.com/EN/Y2026/V85/I6/258

Figures/Tables 5

Fig. 1. (a) Schematic illustration for the synthesis process of NiSe2-O-CQDs. XRD patterns of NiSe2 (b) and NiSe2-O-CQDs-10:1 (c) fitted by the Rietveld Refinement (RR) analysis. HRTEM (d) and EDX elemental mapping (e) images of the NiSe2-O-CQDs-10:1. XPS spectra of Ni 2p (e) and Se 3d (f) for NiSe2, O-CQDs and NiSe2-O-CQDs-X:1 (X = 5, 10 and 20).

Fig. 2. XAS analysis of the NiSe2 and NiSe2-O-CQDs-10:1. (a) XANES spectra at Ni K-edge (insert: the enlarged image). (b) FT-EXAFS spectra of Ni R space. (c) XANES spectra at Se K-edge (insert: the enlarged image). (d) FT-EXAFS spectra of Se R space. WT of Ni K-edge EXAFS (e) and Se K-edge EXAFS (f) for NiSe2, NiSe2-O-CQDs-10:1 and the reference samples, respectively.

Fig. 3. (a) RRDE polarization curves of NiSe2, O-CQDs, and NiSe2-O-CQDs-X:1 (X = 5, 10, 20) recorded at 1600 rpm in O2-saturated 0.1 mol L-1 KOH. (b) H2O2 selectivity and electron transfer number (n) against applied potentials. (c) the corresponding Tafel plots. (d) The calculated transfer electron number (n) of NiSe2, O-CQDs, and NiSe2-O-CQDs-X:1 (X = 5, 10, 20) based on the Koutecky-Levich equation. In-situ ATR-IR spectra of NiSe2-O-CQDs-10:1 catalyst in O2-saturated 0.1 mol L-1 KOH electrolyte at various applied potentials (e1) and zoomed portion of OOHad intermediate emergences (e2). (f) Schematic illustration of 2e- transfer associative mechanism to produce H2O2.

Fig. 4. DFT calculations. (a) Configuration of O2 molecules adsorbed at Ni1 sites in NiSe2 and NiSe2-O-CQDs, respectively. The fluorescent green, silvery, red, brown and white balls represent Se, Ni, O, C and H atoms, respectively. (b) Comparison of binding energy for O2 molecules adsorbed at different sites (Ni and Se atoms). (c) Gibbs free energy diagram of 2e- ORR pathway at U = 0.7 V. Gibbs free energy diagram of 2e- and 4e- ORR pathways for NiSe2-O-CQDs (d) and NiSe2 (e) at U = 0 V. (f) Electron density difference analysis of NiSe2 and NiSe2-O-CQDs, yellow (cyan) represents the charge accumulation (deletion). Total density of states and PDOS for NiSe2-O-CQDs (g) and NiSe2 (h). COHP analysis of NiSe2-O-CQDs (i) and NiSe2 (j).

Fig. 5. Electrochemical production of H2O2 using a continuous flow cell. (a) Schematic diagram of the assembled flow cell. (b) H2O2 yield and Faraday efficiency recorded at different applied potentials. (c) Cumulative H2O2 yield of NiSe2-O-CQDs-10:1 for 100 h and O-CQDs for 55 h. (d) Stability test (chronopotentiometry) of NiSe2-O-CQDs-10:1 and O-CQD. (e) H2O2 yield and Faraday efficiency of NiSe2-O-CQDs-10:1 in comparison with recently reported catalysts (The H2O2 production yield for catalysts, such as o-CQD-3, Ni-N-C, Bi/PNC-4, Co-N-C, Ni-N2O2/C, and CoPc@OCW obtained in a flow cell with 0.1 mol L-1 KOH. For c-MOF Ni-250, the H2O2 production yield was obtained in a single-chamber cell with 0.1 mol L-1 KOH; for the COF-366-Co, DCDs, S10RGO, 2D Al-MOF, an H-type cell with 0.1 mol L-1 KOH was used; for the NiSe2-O-CQDs-10:1 (this work), SC-1, Ni-SAC, Sb-NSCF, Zn2SnO4/SnO2, and Sb-NSCF, a flow cell with 1 mol L-1 KOH was used. (f) Digital photographs of Rh B and MB during the decomposition process. (g) Degradation performance of Rhodamine B and Methylene Blue by the catholyte after electrolysis for 1 h.

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O-bridged NiSe₂/CQDs composite synergistically triggers interfacial electrons transfer to promote H₂O₂ electrosynthesis

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