Artificial modulated Lewis pairs for highly efficient alkaline hydrogen production

Xiao, Zehao; Yang, Mei; Liu, Canhui; Wang, Bowen; Zhang, Shilin; Liu, Jingyan; Xu, Zonglin; Gao, Ruijie; Zou, Ji‐Jun; Tang, Aidong; Yang, Huaming

doi:10.1016/j.nanoen.2022.107233

Cited by 24 publications

(18 citation statements)

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“…As shown in Figure S11, XPS survey spectra demonstrate that CoMoO 4 /NF is predominantly constituted of O, Mo, and Co elements, and there is no peak of Co δ+ species, indicating that Co δ+ is due to the Co–P bond formation. Furthermore, the peak intensity of the Co δ+ specie in CoP 4 /CoMoO 4 /NF is weaker than that in Ni(PO 3 ) 2 -CoP 4 /CoMoO 4 /NF, indicating that the multi-interface promotes the Co δ+ species formation, thereby optimizing the intermediate adsorption/desorption properties of the reactants and lowering the reaction energy barrier for H 2 O activation. , As shown in Figure e, the Mo 3d XPS spectra of two catalysts, the peaks at 231.78 and 234.88 eV, are assigned to the 3d 5/2 and 3d 3/2 of Mo 6+ ions. , For P 2p spectrum (Figure f), these peaks at 134.13 and 135.35 eV are attributed to the P–O, which belonged to the Ni(PO 3 ) 2 phase (the P–O peak of CoP 4 /CoMoO 4 /NF can be attributed to phosphates formed on the surface because of its exposure to air), respectively, whereas other peaks of 129.50 and 130.30 eV belonged to metal phosphides (Co–P) . Compared with Ni(PO 3 ) 2 /NF catalysts, binding energy of P–O in the Ni(PO 3 ) 2 -CoP 4 /CoMoO 4 /NF catalyst peak is shifted negatively 0.30 eV, demonstrating the strong electronic interaction and charge redistribution of the interface. , In Figure S13, the high-resolution O 1s region shows that three peaks are associated with M–O, H–O, and P–O, respectively .…”

Section: Resultsmentioning

confidence: 96%

“…Therefore, the Ni(PO 3 ) 2 -CoP 4 /CoMoO 4 /NF catalyst has excellent HER performance in freshwater alkaline media and maintains high stability in harsh environments (alkaline natural seawater electrolyte). The mechanism of alkaline HER of Ni(PO 3 ) 2 -CoP 4 /CoMoO 4 /NF catalyst is shown in Figure c, which is promoted by the Ni(PO 3 ) 2 , and CoP 4 /CoMoO 4 can promote the Volmer step, the mechanism of Ni(PO 3 ) 2 -CoP 4 /CoMoO 4 heterointerface is Volmer-Tafel, and the rate-determining step is the H 2 desorption process for hydrogen. Effective collaboration can significantly affect the HER performance.…”

Section: Resultsmentioning

confidence: 96%

“…Tafel slopes of Ni(PO 3 ) 2 -CoP 4 /CoMoO 4 /NF show 27.75 mV·dec –1 , that is less than CoP 4 /CoMoO 4 /NF (60.05), Ni(PO 3 ) 2 /NF (98.94), CoMoO 4 /NF (110.68), NF (106.51), and 20 wt % Pt/C/NF (56.15), confirming superior HER kinetics. It is well known that the basic HER process includes the primary discharge step and subsequent steps of desorption or recombination, and such an extremely low Tafel slope suggests a typical Volmer–Tafel mechanism pathway of alkaline HER. − Furthermore, 20 wt % Pt/C/NF continuously generated a large number of H 2 bubbles during HER, but most of the bubbles stuck to the surface causing a severe ohmic drop, resulting in an excessive Tafel slope for 20 wt % Pt/C/NF, , as shown in Figure S13. As shown in Figure S14, the j 0 value of the Ni(PO 3 ) 2 -CoP 4 /CoMoO 4 /NF catalyst is 1.89 mA·cm –2 , which outperforms 1.55, 0.40, and 0.15 mA·cm –2 of CoP 4 /CoMoO 4 /NF, Ni(PO 3 ) 2 /NF, and CoMoO 4 /NF, respectively.…”

Section: Resultsmentioning

confidence: 99%

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Multiple Interface Ni(PO₃)₂-CoP₄/CoMoO₄ Nanorods for Highly Efficient Hydrogen Evolution in Alkaline Water/Seawater Electrolysis

Yang

Zhang

Shi

et al. 2022

ACS Sustainable Chem. Eng.

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The key to the development of non-noble metal catalysts with high activity and durability for the hydrogen evolution reaction (HER) in alkaline water/seawater conditions is to construct multi-interface electrocatalysts. Herein, the CoMoO4 nanorod arrays grown on foam nickel (NF) was first prepared by a hydrothermal method. Then, Ni(PO3)2-CoP4 with multi-interface was prepared by soaking the nanorod arrays into a nickel nitrate solution and then by phosphating via chemical vapor deposition. The Ni(PO3)2-CoP4/CoMoO4/NF electrode exhibits superior HER electrocatalytic performance under alkaline conditions with an ultralow overpotential of 79 mV@100 mA·cm–2, which outperforms other reported earth–abundant transition-metal phosphide catalysts. It also maintains long-term durability in alkaline water/seawater electrolytes in 60 h at a constant 100 mA·cm–2. In the alkaline natural seawater electrolyte, Ni(PO3)2-CoP4/CoMoO4/NF (−)||NiFe LDH (+) pair has good long-term stability of 60 h for the voltage of only 1.60 V@100 mA·cm–2. The excellent performance is attributed to the plentiful active sites and the rapid electron-transfer rate. This work affords a new path to rationalize the design strategy of low-cost and multi-interface 3D catalysts for alkaline water/seawater electrolysis.

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Section: Resultsmentioning

confidence: 96%

Section: Resultsmentioning

confidence: 96%

Section: Resultsmentioning

confidence: 99%

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Multiple Interface Ni(PO₃)₂-CoP₄/CoMoO₄ Nanorods for Highly Efficient Hydrogen Evolution in Alkaline Water/Seawater Electrolysis

Yang

Zhang

Shi

et al. 2022

ACS Sustainable Chem. Eng.

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“…In addition, the synergistic effect of heterogeneous components can also enhance the activity of the reconstructed species. Yang et al synthesized broccoli‐like hierarchical Ni 2 P‐Ni(PO 3 ) 2 nanoparticles on vertical monocrystalline NiMoO 4 nanorods, [ 152 ] which effectively integrate artificial frustrated Lewis pairs (FLPs) after reconstruction process. As shown in Figure 15f, dissolution of MoO x further exposed more Ni sites as Lewis base sites to promote the adsorption of H* during the Tafel step, while hydroxyl ligands in situ formed on the surface of the loaded nanoparticles as Lewis acid sites to boost the activation of H 2 O molecules.…”

Section: Reconstruction Strategies For Her Electrocatalystsmentioning

confidence: 99%

“…f) Evolution of Ni-P-O/ MoO x to generate Ni-P-O during HER process and enhanced mechanism of catalytic activity Ni-P-O for alkaline HER. Reproduced with permission [152]. Copyright 2022, Elsevier.…”

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confidence: 99%

Surface Reconstruction of Water Splitting Electrocatalysts

Zeng

Zhao

Huang

et al. 2022

Advanced Energy Materials

154

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Gibbs free energy (ΔG) of water splitting reaction is 237.2 kJ mol −1 , corresponding to a theoretical voltage of 1.23 V. [3] However, the existence of electrochemical/concentration polarization and solution resistance can increase the actual voltage of water electrolysis to much beyond 1.23 V. Particularly, the OER involves a complicated four-electron transfer process, which results in a sluggish kinetics thus has long been the bottleneck. [4] Therefore, it is necessary to explore efficient and robust electrocatalysts to reduce the overpotential of water electrolysis and the extra electric energy consumption. Although noble electrocatalysts, such as Pt, RuO 2 and IrO 2 , are recognized as the most efficient electrocatalysts for water electrolysis, their high scarcity and instability severely impede large-scale applications. [5] Recently, considerable effort has been focused on nonnoble transition-metal materials as viable alternatives for water splitting. Understanding the intrinsic catalytic mechanism and real active sites of these catalysts will benefit the rational design and application of high-efficiency catalysts.With the development of in situ characterization technologies, more reports have revealed that the original electrocatalyst (so-called "pre-catalyst") surface sites would undergo dynamic reconstruction and transform into real reactive species. [6] This in situ reconstruction process could tune the electrocatalytic behaviors such as adsorption, activation, and desorption, thus improving the catalytic performance. [7] On this basis, many researchers utilized the pre-reconstruction of electrocatalysts to obtain a large number of active species for the catalytic reactions. [8] It has been found that the intrinsic properties of the pre-catalysts, such as composition, atomic arrangement, porosity, and crystallinity, would affect the reconstruction rate, reconstruction degree, and catalytic activity of the reconstructed species. [9] Moreover, the reaction conditions also affect the reconstruction process, such as electrochemical operation, applied potential, electrolyte concentration, and pH. [6a] Therefore, tuning the reconstruction process to generate abundant active sites with high intrinsic activity is an effective strategy to boost the catalytic performance of electrocatalysts.Although some influential review articles on the reconstruction of catalysts during water electrolysis have emerged, [10] most of them focus on the discovery and characterization of the reconstruction phenomenon, less on the regulation of the reconstruction process. In addition, reconstructed catalysts for Water electrolysis is regarded as an efficient and green method to produce hydrogen gas, a clean energy carrier that holds the key to solving global energy problems. So far, the efficiency and large-scale application of water electrolysis are restricted by the electrocatalytic activity of applied catalysts. Recently, the reconstruction phenomenon of electrocatalysts during a catalytic reaction has been discovered, which ...

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Modulation of Electron Structure and Dehydrogenation Kinetics of Nickel Phosphide for Hydrazine‐Assisted Self‐Powered Hydrogen Production in Seawater

Chi

Guo

Mao

et al. 2023

Adv Funct Materials

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The electrocatalytic production of hydrogen from seawater provides a low‐cost way to realize energy conversion, but is restricted by high potential for seawater electrolysis and the chlorine oxidation reaction (ClOR) at the anode. Here, the self‐growth of Mo‐doped Ni2P nanosheet arrays with rich P vacancies on molybdenum‐nickel foam (MNF) (Mo‐Ni2Pv@MNF) is reported as bifunctional catalyst for Cl‐free hydrogen production by coupling hydrogen evolution reaction (HER) with hydrazine oxidation reaction (HzOR) in seawater. Impressively, the Mo‐Ni2Pv@MNF electrode as bifunctional catalyst has an excellent activity for overall hydrazine splitting (OHzS) with an ultralow voltage of only 571 mV at 1000 mA cm−2 and can maintain stability for an ultra‐long time of 1000 h at 100 mA cm−2. Moreover, integration of OHzS into self‐assembled hydrazine fuel cells (DHzFC) or solar cells can enable the self‐powered H2 production. The industrial hydrazine sewage as feed for the above eletrolysis system can be degraded to ≈5 ppb rapidly. Density functional thoery calculations demonstrate that the electronic structure modulation induced by P vacancies and Mo doping can not only achieve thermoneutral ΔGH* for hydrogen evolution reaction but also enhance dehydrogenation kinetics from *N2H4 to *NHNH2 for HzOR, achieving enhanced dehydrogenation kinetics.

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Artificial modulated Lewis pairs for highly efficient alkaline hydrogen production

Cited by 24 publications

References 58 publications

Multiple Interface Ni(PO₃)₂-CoP₄/CoMoO₄ Nanorods for Highly Efficient Hydrogen Evolution in Alkaline Water/Seawater Electrolysis

Multiple Interface Ni(PO₃)₂-CoP₄/CoMoO₄ Nanorods for Highly Efficient Hydrogen Evolution in Alkaline Water/Seawater Electrolysis

Surface Reconstruction of Water Splitting Electrocatalysts

Modulation of Electron Structure and Dehydrogenation Kinetics of Nickel Phosphide for Hydrazine‐Assisted Self‐Powered Hydrogen Production in Seawater

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Artificial modulated Lewis pairs for highly efficient alkaline hydrogen production

Cited by 24 publications

References 58 publications

Multiple Interface Ni(PO3)2-CoP4/CoMoO4 Nanorods for Highly Efficient Hydrogen Evolution in Alkaline Water/Seawater Electrolysis

Multiple Interface Ni(PO3)2-CoP4/CoMoO4 Nanorods for Highly Efficient Hydrogen Evolution in Alkaline Water/Seawater Electrolysis

Surface Reconstruction of Water Splitting Electrocatalysts

Modulation of Electron Structure and Dehydrogenation Kinetics of Nickel Phosphide for Hydrazine‐Assisted Self‐Powered Hydrogen Production in Seawater

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Multiple Interface Ni(PO₃)₂-CoP₄/CoMoO₄ Nanorods for Highly Efficient Hydrogen Evolution in Alkaline Water/Seawater Electrolysis

Multiple Interface Ni(PO₃)₂-CoP₄/CoMoO₄ Nanorods for Highly Efficient Hydrogen Evolution in Alkaline Water/Seawater Electrolysis