The effective non‐precious metal catalysts toward the oxygen evolution reaction (OER) are highly desirable for electrochemical water splitting. Herein, we prepare a novel glass‐ceramic (Ni1.5Sn@triMPO4) by embedding crystalline Ni1.5Sn nanoparticles into amorphous trimetallic phosphate (triMPO4) matrix. This unique crystalline‐amorphous nanostructure synergistically accelerates the surface reconstruction to active Ni(Fe)OOH, due to the low vacancy formation energy of Sn in glass‐ceramic and high adsorption energy of PO43− at the VO sites. Compared to the control samples, this dual‐phase glass‐ceramic exhibits a remarkably lowered overpotential and boosted OER kinetics after surface reconstruction, rivaling most of state‐of‐the‐art electrocatalysts. The residual PO43− and intrinsic VO sites induce redistribution of electron states, thus optimizing the adsorption of OH* and OOH* intermediates on metal oxyhydroxides and promoting the OER activity.
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.
The development of Pt‐free catalysts for the alkaline hydrogen evolution reaction (HER), which is widely used in industrial scale water‐alkali electrolyzers, remains a contemporary and pressing challenge. Ruthenium (Ru) has excellent water‐dissociation abilities and could be an alternative water splitting catalyst. However, its large hydrogen binding energy limits HER activity. Here, a new approach is proposed to boost the HER activity of Ru through uniform loading of Ru nanoparticles on triazine‐ring (C3N3)‐doped carbon (triNC). The composite (Ru/triNC) exhibits outstanding HER activity with an ultralow overpotential of ≈2 mV at 10 mA cm−2; thereby making it the best performing electrocatalyst hitherto reported for alkaline HER. The calculated metal mass activity of Ru/triNC is >10 and 15 times higher than that of Pt/C and Pt/triNC. Both theoretical and experimental studies reveal that the triazine‐ring is a good match for Ru to weaken the hydrogen binding on Ru through interfacial charge transfer via increased contact electrification. Therefore, Ru/triNC can provide the optimal hydrogen adsorption free energy (approaching zero), while maintaining the strong water‐dissociation activity. This study provides a new avenue for designing highly efficient and stable electrocatalysts for water splitting.
• Hierarchical N-doped porous carbons (NPCs) with large surface area and controllable N-doping are synthesized by ball milling, followed by pyrolysis. • As a Zn-air battery cathode, NPCs have comparable discharge performance to precious metal catalysts and more stability. • NPCs also exhibit an excellent specific capacity and cycling stability when used as supercapacitor electrodes. ABSTRACT Nitrogen-doped carbon materials with a large specific surface area, high conductivity, and adjustable microstructures have many prospects for energy-related applications. This is especially true for N-doped nanocarbons used in the electrocatalytic oxygen reduction reaction (ORR) and supercapacitors. Here, we report a low-cost, environmentally friendly, large-scale mechano
The inferior conductivity and large volume expansion impair the widespread applications of metal oxide‐based anode materials for lithium‐ion batteries. To address these issues, herein an efficient strategy of structural engineering is proposed to improve lithium storage performance of hierarchical CoO nanospheres wrapped by graphene via controllable S‐doping (CoOS0.1 @ G). S‐doping promotes the Li+ diffusion kinetics of CoO by expanding the interplanar spacing of CoO, lowering the activation energy, and improving the pseudocapacitance contribution. Meanwhile, the electronic structure of CoO is adjusted by S‐doping as confirmed by density functional theory calculations, thus enhancing the conductivity. Finite element analysis reveals that the produced Li2S during lithiation improves the structural stability of the S‐doped electrode, which is further confirmed by experimental observation. As expected, CoOS0.1 @ G exhibits excellent lithium storage performance with an initial discharge capacity of 1974 mAh g−1 at 100 mA g−1, and high discharge capacity of 1573 mAh g−1 after 400 cycles at 500 mA g−1. It is believed that the insights into the structural doping enlighten research to explore other metal oxides for fast and stable Li ion storage.
Developing
high-performance and cost-effective bifunctional electrocatalysts
for water splitting is the key to large-scale hydrogen production.
How to achieve higher performance with a lower amount of noble metal
is still a major challenge. Herein, using a facile wet-chemistry strategy,
we report the ultralow amount loading of ruthenium (Ru) on porous
nickel foam (NF) as a highly efficient bifunctional electrocatalyst
for water splitting. Theoretical simulations reveal that the coupling
effect of Ru and Ni can significantly reduce the d-band center of
the composite. The Ru-modified NF exhibits a very high level of HER
activity with only 0.3 wt% of Ru, far surpassing commercial Pt/C.
It only requires an extremely low overpotential (η10) of 10 mV to achieve a current density of 10 mA cm–2 in alkaline solution and a quite low Tafel slope of 34 mV dec–1. This catalyst also shows remarkable performance
for overall water splitting with a low voltage of 1.56 V at 10 mA
cm–2. These findings indicate the potential of this
material in water–alkali electrolyzers, providing a new approach
for fabrication of low-cost advanced electrocatalysts.
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