Cobalt-Nanoparticle-Decorated Cobalt–Molybdenum Bimetal Oxides Embedded in Flower-like N-Doped Carbon as a Durable and Efficient Electrocatalyst for Oxygen Evolution Reaction

Zhang, Yanan; Ye, Wenlong; Fan, Jinchen; Çeçen, Volkan; Shi, Peipei; Min, Yulin; Xu, Qing

doi:10.1021/acssuschemeng.1c02472

Cited by 35 publications

(10 citation statements)

References 73 publications

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“…33 However, the peak of graphitic carbon is not shown in the PXRD pattern because of the high crystallinity of metal phosphide. 34 The BET surface area and pore diameter of 3D Cu-MOF and Cu 3 P/Cu@NC heterostructure were measured through the N 2 adsorption−desorption isotherm having surface areas of 12.88 and 139.8 m 2 g −1 and pore diameters of 1.86 and 1.91 nm, respectively, as shown in Figure S1. After phosphorization, the total pore diameter and BET surface area of the Cu 3 P/ Cu@NC heterostructure was increased as compared to Cu-MOF due to the increased carbon content of materials.…”

Section: Resultsmentioning

confidence: 99%

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Phosphorization Engineering on a MOF-Derived Metal Phosphide Heterostructure (Cu/Cu₃P@NC) as an Electrode for Enhanced Supercapacitor Performance

Hussain,

Abbas,

Ansari

et al. 2023

Inorg. Chem.

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A highly conductive and rationally constructed metal–organic framework (MOF)-derived metal phosphide with a carbonaceous nanostructure is a meticulous architecture toward the development of electrode materials for energy storage devices. Herein, we report a facile strategy to design and construct a new three-dimensional (3D) Cu-MOF via a solvent diffusion method at ambient temperature, which was authenticated by a single-crystal X-ray diffraction study, revealing a novel topology of (2,4,7)-connected three-nodal net named smm 4. Nevertheless, the poor conductivity of pristine MOFs is a major bottleneck hindering their capacitance. To overcome this, we demonstrated an MOF-derived Cu 3 P/Cu@NC heterostructure via low-temperature phosphorization of Cu-MOF. The electronic and ionic diffusion kinetics in Cu 3 P/Cu@NC were improved due to the synergistic effects of the heterostructure. The as-prepared Cu 3 P/Cu@NC heterostructure electrode delivers a specific capacity of 540 C g–1 at 1 A g–1 with outstanding rate performance (190 C g–1 at 20 A g–1) and cycle stability (91% capacity retention after 10,000 cycles). Moreover, the assembled asymmetric solid-state supercapacitor (ASC) achieved a high energy density/power density of 45.5 Wh kg–1/7.98 kW kg–1 with a wide operating voltage (1.6 V). Long-term stable capacity retention (87.2%) was accomplished after 5000 cycles. These robust electrochemical performances suggest that the Cu 3 P/Cu@NC heterostructure is a suitable electrode material for supercapacitor applications.

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Section: Resultsmentioning

confidence: 99%

“…65–9743) . However, the peak of graphitic carbon is not shown in the PXRD pattern because of the high crystallinity of metal phosphide …”

Section: Resultsmentioning

confidence: 99%

Phosphorization Engineering on a MOF-Derived Metal Phosphide Heterostructure (Cu/Cu₃P@NC) as an Electrode for Enhanced Supercapacitor Performance

Hussain,

Abbas,

Ansari

et al. 2023

Inorg. Chem.

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“…To better adapt to the practical applications, low cost, environmental friendliness and other problems cannot be ignored. [197][198][199][200][201][202][203][204] We need to develop simple, universal and large-scale production techniques to meet these needs. So far, there is few reports about the synthesis route for mesoporous carbon-based films by one step.…”

Section: Discussionmentioning

confidence: 99%

Interfacial Assembly of Functional Mesoporous Carbon‐Based Materials into Films for Batteries and Electrocatalysis

Xie

et al. 2022

Adv Materials Inter

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However, to better integrate those energy sources and applications, proper energy storage and conversion systems are vital. Tremendous efforts have been made to the development of energy systems, mainly including batteries (e.g., lithium batteries, fuel cells) and electrocatalysis (e.g., solid electrolyte, water splitting). [11][12][13][14][15] Nevertheless, these energy systems still face some tough problems and challenges. To realize large scale production, low cost and high efficiency, the development of advanced materials in these energy systems is crucial and indispensable.Porous materials, due to their unique properties and a wide range of applications, have always been a hot topic in research. [16][17][18][19][20] According to the International Union of Pure and Applied Chemistry (IUPAC), porous material can be divided into three categories by their pore sizes. That is, microporous when pore size is below 2 nm, mesoporous (2-50 nm) and macroporous (>50 nm). Among them, mesoporous carbon materials have been regarded as promising candidates when applied in many energy systems owing to their large surface area and pore volumes, tunable pore size and channels. [21][22][23] All of these characteristics have their own merits, which can address certain issues in different energy storage and conversion systems. [24][25][26][27] First of all, the large surface area, especially when combined with particular functional groups or certain atoms doping, can provide much more reaction sites and active absorption sites during surface or interface-related reaction such as electrocatalytic process. [28,29] Secondly, large pore volumes can not only accommodate more guest materials as an excellent host but also buffer the volume change and relax the strain during repeated electrochemical reactions in many batteries. [30] Thirdly, the tunable pore size and channels can accelerate ions and intermediate species transport, which improve the reaction rate and assure the complete conversion of reaction. [31,32] Moreover, these mesopores with appropriate size have physical and chemical confinement effect to avoid the loss or aggregation of active materials in some energy storage devices and catalytic processes.On the other hand, in recent years, many freestanding 2D films based on graphene, black phosphorus or transition metal carbide MXenes have been synthesized. [33][34][35] 2D films,

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“…Based on this, we notice a family of honeycomb-like ABMo 3 O 8 with high conductivity. − Crystallographically, ABMo 3 O 8 has a hexagonal lattice structure alternating AB layers and Mo layers, belonging to the P 63 mc space group. − Within the AB layer, A and B represent 3d TM cations such as Mn, Fe, Co, Ni, etc. and occupy the coordination of O h and T d , respectively.…”

mentioning

confidence: 92%

“…Although Liu’s group identified that the T d Co was an active site through theoretical calculations, there is still no experimental evidence to support this conclusion . Furthermore, most existing studies have focused on heterojunctions of metal/metal oxide and Co 2 Mo 3 O 8 , limiting the evaluation of the intrinsic activity of Co 2 Mo 3 O 8 . − Therefore, a clear consensus on the fundamental understanding of their structure–property relationships has yet to be reached.…”

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confidence: 99%

Simultaneous Activation of Different Coordination Sites in Single-Phase FeCoMo₃O₈ for the Oxygen Evolution Reaction

Hao,

Li,

Huang

et al. 2023

ACS Energy Lett.

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ABMo 3 O 8 is an emerging oxygen evolution reaction (OER) electrocatalyst, exhibiting dual coordination sites for transition metals with good conductivity. However, it is unclear which sites are active for the OER and how to activate them both. Herein, we demonstrated experimentally that only tetrahedral (T d ) Co sites are highly active in Co 2 Mo 3 O 8 , and octahedral (O h ) sites are activated by introducing Fe. Various synchrotron X-ray based spectroscopies confirmed the allocation of Co 2+ at T d and Fe 2+ at O h sites. The dual activation of different sites improved the OER efficiency with overpotentials of 308 mV@10 mA cm −2 and 361 mV@100 mA cm −2 . This unique structure with corner-shared T d Co and O h Fe in high spin states increases the active site numbers, produces synergistic effects, optimizes the adsorption of intermediates, and creates an unobstructed spin channel for electron transfer. This work provides an effective strategy to design a pair of OER catalysts by coordination engineering.T he oxygen evolution reaction (OER) plays a crucial role in converting renewable energy into chemical fuels. 1−4 Among candidates, 3d transition-metal oxidebased catalysts (TMOs) have garnered remarkable attention due to their low cost and promising performance. 5−8 These crystal structures of TMOs are principally constructed based on octahedral (O h ) MO 6 units or/and tetrahedral (T d ) MO 4 units. 9 However, researchers have found that usually only one coordination site is the dominant active site. For example, the perovskite only contains O h coordination transition metal (TM), 5,10 while YBaCo 4 O 7.3 contains only T d TM as active sites. 11 Although spinel coexists with T d and O h sites, only O h sites play the leading role. 12−15 This severely limits the utilization of TM and even restricts a possible fast mechanism. In addition, the poor conductivity of most TMOs is also an obstacle to their OER performance. 16,17 Based on this, we notice a family of honeycomb-like ABMo 3 O 8 with high conductivity. 18−21 Crystallographically, ABMo 3 O 8 has a hexagonal lattice structure alternating AB layers and Mo layers, belonging to the P 63 mc space group. 22−25 Within the AB layer, A and B represent 3d TM cations such as Mn, Fe, Co, Ni, etc. and occupy the coordination of O h and T d , respectively. These two types of AO 6 and BO 4 corner-sharing polyhedra interchangeably connect to form honeycomb-like layers in the ab-plane, separated by the O h MoO 6 layers. In the Mo layer, three Mo 4+ (4d 2 ) ions combine to form unique spinsinglet trimers. This structure results in shorter intracluster

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Cobalt-Nanoparticle-Decorated Cobalt–Molybdenum Bimetal Oxides Embedded in Flower-like N-Doped Carbon as a Durable and Efficient Electrocatalyst for Oxygen Evolution Reaction

Cited by 35 publications

References 73 publications

Phosphorization Engineering on a MOF-Derived Metal Phosphide Heterostructure (Cu/Cu₃P@NC) as an Electrode for Enhanced Supercapacitor Performance

Phosphorization Engineering on a MOF-Derived Metal Phosphide Heterostructure (Cu/Cu₃P@NC) as an Electrode for Enhanced Supercapacitor Performance

Interfacial Assembly of Functional Mesoporous Carbon‐Based Materials into Films for Batteries and Electrocatalysis

Simultaneous Activation of Different Coordination Sites in Single-Phase FeCoMo₃O₈ for the Oxygen Evolution Reaction

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Cobalt-Nanoparticle-Decorated Cobalt–Molybdenum Bimetal Oxides Embedded in Flower-like N-Doped Carbon as a Durable and Efficient Electrocatalyst for Oxygen Evolution Reaction

Cited by 35 publications

References 73 publications

Phosphorization Engineering on a MOF-Derived Metal Phosphide Heterostructure (Cu/Cu3P@NC) as an Electrode for Enhanced Supercapacitor Performance

Phosphorization Engineering on a MOF-Derived Metal Phosphide Heterostructure (Cu/Cu3P@NC) as an Electrode for Enhanced Supercapacitor Performance

Interfacial Assembly of Functional Mesoporous Carbon‐Based Materials into Films for Batteries and Electrocatalysis

Simultaneous Activation of Different Coordination Sites in Single-Phase FeCoMo3O8 for the Oxygen Evolution Reaction

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Phosphorization Engineering on a MOF-Derived Metal Phosphide Heterostructure (Cu/Cu₃P@NC) as an Electrode for Enhanced Supercapacitor Performance

Phosphorization Engineering on a MOF-Derived Metal Phosphide Heterostructure (Cu/Cu₃P@NC) as an Electrode for Enhanced Supercapacitor Performance

Simultaneous Activation of Different Coordination Sites in Single-Phase FeCoMo₃O₈ for the Oxygen Evolution Reaction