Regulating the Local Spin State and Band Structure in Ni<sub>3</sub>S<sub>2</sub> Nanosheet for Improved Oxygen Evolution Activity

Wang, Zongpeng; Shen, Shijie; Lin, Zhiping; Tao, Weiying; Zhang, Qinghua; Meng, Fanqi; Gu, Lin; Zhong, Wen‐De

doi:10.1002/adfm.202112832

Cited by 119 publications

(74 citation statements)

References 49 publications

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“…Experimental and theoretical calculations have revealed that changes in the adsorption of oxygen-containing intermediates are key to rate limiting in catalytic reactions. 47 The hydrogenation of OH to water increased significantly in the Ti–N 4 –Gr/V 2 C and Cr–N 4 –Gr/V 2 C catalysts, which is not favorable for the ORR process. The hydrogenation *OH to H 2 O is the rate-determining step for Ti–N 4 –Gr/V 2 C, Cr–N 4 –Gr/V 2 C, Mn–N 4 –Gr/V 2 C, Fe–N 4 –Gr/V 2 C, Co–N 4 –Gr/V 2 C, Ni–N 4 –Gr/V 2 C, and Cu–N 4 –Gr/V 2 C. Among them, Ni–N 4 –Gr/V 2 C and Co–N 4 –Gr/V 2 C exhibited high ORR performance with theoretical overpotentials of 0.32 and 0.45 V, respectively; Co–N 4 –Gr/V 2 C showed a catalytic activity comparable to that of the Pt/C catalyst.…”

Section: Resultsmentioning

confidence: 92%

Rational design of M–N₄–Gr/V₂C heterostructures as highly active ORR catalysts: a density functional theory study

et al. 2022

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Section: Resultsmentioning

confidence: 92%

Rational design of M–N₄–Gr/V₂C heterostructures as highly active ORR catalysts: a density functional theory study

et al. 2022

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“…Compared with the fresh NiS x , NiS x -R demonstrates weaker peaks ascribed to metal-sulfur bindings (Ni-S) at 162 eV (S 2 p 3/2 ) and 163 eV (S 2 p 1/2 ), and a stronger S-O peak at ~168 eV (Fig. 3h ), suggesting the surface oxidization during the CV activation 4 , 39 . Figure 3i shows the fitting peaks of Se 3 d at 55 and 54 eV, agreeing well with the chemical states of Se 3 d 3/2 and Se 3 d 5/2 .…”

Section: Resultsmentioning

confidence: 99%

Coordination environment tuning of nickel sites by oxyanions to optimize methanol electro-oxidation activity

et al. 2022

Nat Commun

114

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To achieve zero-carbon economy, advanced anode catalysts are desirable for hydrogen production and biomass upgrading powered by renewable energy. Ni-based non-precious electrocatalysts are considered as potential candidates because of intrinsic redox attributes, but in-depth understanding and rational design of Ni site coordination still remain challenging. Here, we perform anodic electrochemical oxidation of Ni-metalloids (NiPx, NiSx, and NiSex) to in-situ construct different oxyanion-coordinated amorphous nickel oxyhydroxides (NiOOH-TOx), among which NiOOH-POx shows optimal local coordination environment and boosts electrocatalytic activity of Ni sites towards selective oxidation of methanol to formate. Experiments and theoretical results demonstrate that NiOOH-POx possesses improved adsorption of OH* and methanol, and favors the formation of CH3O* intermediates. The coordinated phosphate oxyanions effectively tailor the d band center of Ni sites and increases Ni-O covalency, promoting the catalytic activity. This study provides additional insights into modulation of active-center coordination environment via oxyanions for organic molecules transformation.

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“…Producing H 2 through a green and sustainable way plays a vital role in the upgrading of energy sector and the fighting of global warming, [1,2] Electrocatalytically water splitting holds encouraging prospect for the production of hydrogen, where electrocatalysts are required to boost the electron-proton coupled transportation. [3][4][5][6][7] Transition metals and their complexes in the d-electron area of the periodic table constitute a large portion of the catalyst library for the hydrogen evolution reaction (HER), [8][9][10][11][12][13][14] taking advantage of the versatile interaction between the empty d band…”

Section: Introductionmentioning

confidence: 99%

Realizing Negatively Charged Metal Atoms through Controllable d‐Electron Transfer in Ternary Ir₁₋_xRh_xSb Intermetallic Alloy for Hydrogen Evolution Reaction

Lin

Xiao

Huang

et al. 2022

Advanced Energy Materials

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with the H 1s band. Among these catalysts, noble metals such as Pt and Ir exhibit the best HER activity locating at the top of the volcano plot, due to the Sabatier's principle. [15][16][17] However, the earth abundance of noble metals is an inevitable and insurmountable obstacle for the practical application of noble metals. Alloying noble metals with high-abundance metals is a possible way to reducing the usage of noble metals while sustaining their high catalytical performance, which remains a challenging mission. [18][19][20] Metal sites in complexes usually exhibit insufficient adsorption ability for active *H species, due to the Coulomb repulsion. Suffering from the insufficient adsorption, the metal sites in many catalysts are inert. For example, the Mo sites in MoX 2 (X = S, Se) are inactive for HER. [21][22][23] To enhance the HER performance of metal sites in complex, novel metal sites with abundant electrons are proposed to strengthen the interaction with *H. Kobayashi et al. reported negatively charged Pt obtained by light doping of W through electrochemical cleaning of core/shell PtW@WO 3 nanoparticles, to enhance the HER activity significantly. [24] The negatively charged Pt atoms provide favorable hydrogen adsorption energy, resulting in an overpotential superior to commercial Pt. As another example, Wei et al. prepared Pt clusters on TiO 2 with rich O vacancies. [25] Reversed charge transfer from TiO 2 to Pt is realized to boost the hydrogen evolution.In this work, we prepared ternary Ir 1−x Rh x Sb intermetallic alloy as highly active electrocatalyst for HER. Due to the large difference in the reduction potential of Ir, Rh, and Sb cations, the Ir 1−x Rh x Sb cannot be synthesized by common solvothermal method. The arc-melting method was then used for the preparation of Ir 1−x Rh x Sb alloy. The electron transfer can be well regulated by modulating the content ratio. Ir atoms in IrSb exhibit negative valence state owing to the electron transfer form Sb to Ir, as revealed by both experimental data and first-principal calculations. The hydrogen adsorption ability of Ir sites is then highly strengthened due to the accumulated electrons. Furthermore, the HER activity of Ir 1−x Rh x Sb is closely modulated and optimized by Rh doping. As a result, the Ir 0.7 Rh 0.3 Sb sample exhibits the best HER activity, with an overpotential of 22 mV at 10 mA cm -2 and a Tafel slope of 47.6 mV dec -1 . This work provides insights into highly active alloys and sheds lights on the utilization of electron-abundant metal atoms.Alloying noble metals with non-noble metals is a promising method to fabricate catalysts, with the advantages of reduced noble metal usage and excellent activity. In this work, electron-abundant Ir/Rh sites, as highly active centers for the hydrogen evolution reaction (HER), are realized by fabricating Ir 1−x Rh x Sb alloys through the arc-melting method. The electron transfer from Sb to Ir/Rh makes the latter negatively charged, leading to considerably optimized adsorption for active H species dur...

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Regulating the Local Spin State and Band Structure in Ni₃S₂ Nanosheet for Improved Oxygen Evolution Activity

Cited by 119 publications

References 49 publications

Rational design of M–N₄–Gr/V₂C heterostructures as highly active ORR catalysts: a density functional theory study

Rational design of M–N₄–Gr/V₂C heterostructures as highly active ORR catalysts: a density functional theory study

Coordination environment tuning of nickel sites by oxyanions to optimize methanol electro-oxidation activity

Realizing Negatively Charged Metal Atoms through Controllable d‐Electron Transfer in Ternary Ir₁₋_xRh_xSb Intermetallic Alloy for Hydrogen Evolution Reaction

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Regulating the Local Spin State and Band Structure in Ni3S2 Nanosheet for Improved Oxygen Evolution Activity

Cited by 119 publications

References 49 publications

Rational design of M–N4–Gr/V2C heterostructures as highly active ORR catalysts: a density functional theory study

Rational design of M–N4–Gr/V2C heterostructures as highly active ORR catalysts: a density functional theory study

Coordination environment tuning of nickel sites by oxyanions to optimize methanol electro-oxidation activity

Realizing Negatively Charged Metal Atoms through Controllable d‐Electron Transfer in Ternary Ir1−xRhxSb Intermetallic Alloy for Hydrogen Evolution Reaction

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Regulating the Local Spin State and Band Structure in Ni₃S₂ Nanosheet for Improved Oxygen Evolution Activity

Rational design of M–N₄–Gr/V₂C heterostructures as highly active ORR catalysts: a density functional theory study

Rational design of M–N₄–Gr/V₂C heterostructures as highly active ORR catalysts: a density functional theory study

Realizing Negatively Charged Metal Atoms through Controllable d‐Electron Transfer in Ternary Ir₁₋_xRh_xSb Intermetallic Alloy for Hydrogen Evolution Reaction