The integration of heterometallic units and nanostructures into metal–organic frameworks (MOFs) used for the oxygen evolution reaction (OER) can enhance the electrocatalytic performance and help ...elucidate underlying mechanisms. We have synthesized a series of stable MOFs (CTGU‐10a1–d1) based on trinuclear metal carboxylate clusters and a hexadentate carboxylate ligand with a (6,6)‐connected nia net. We also present a strategy to synthesize hierarchical bimetallic MOF nanostructures (CTGU‐10a2–d2). Among these, CTGU‐10c2 is the best material for the OER, with an overpotential of 240 mV at a current density of 10 mA cm−2 and a Tafel slope of 58 mV dec−1. This is superior to RuO2 and confirms CTGU‐10c2 as one of the few known high‐performing pure‐phase MOF‐OER electrocatalysts. Notably, bimetallic CTGU‐10b2 and c2 show an improved OER activity over monometallic CTGU‐10a2 and d2. Both DFT and experiments show that the remarkable OER performance of CTGU‐10c2 is due to the presence of unsaturated metal sites, a hierarchical nanobelt architecture, and the Ni–Co coupling effect.
Finding the right balance: The integration of heterometallic clusters and nanostructures into stable hierarchical nanosheet‐based bimetal–organic frameworks allows to increase the oxygen evolution reaction performance of electrocatalysts. The ideal ratio between Co and Ni leads to one of the best performances of pure‐phase MOF–OER electrocatalysts.
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Reported herein are two new polymorphic Co‐MOFs (CTGU‐5 and ‐6) that can be selectively crystallized into the pure 2D or 3D net using an anionic or neutral surfactant, respectively. Each polymorph ...contains a H2O molecule, but differs dramatically in its bonding to the framework, which in turn affects the crystal structure and electrocatalytic performance for hydrogen evolution reaction (HER). Both experimental and computational studies find that 2D CTGU‐5 which has coordinates water and more open access to the cobalt site has higher electrocatalytic activity than CTGU‐6 with the lattice water. The integration with co‐catalysts, such as acetylene black (AB) leads to a composite material, AB&CTGU‐5 (1:4) with very efficient HER catalytic properties among reported MOFs. It exhibits superior HER properties including a very positive onset potential of 18 mV, low Tafel slope of 45 mV dec−1, higher exchange current density of 8.6×10−4 A cm−2, and long‐term stability.
HER choice of surfactants: Two new Co‐MOFs phase‐selected by anionic and neutral surfactants exhibit differential affinity for entrapped water molecules, leading to a difference in the spatial accessibility of active metal sites. A composite material made from such Co‐MOFs shows impressive performance in electrocatalytic hydrogen evolution reaction (HER) as well as long‐term stability.
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Summary
This article presents a two‐layered framework to investigate the output synchronization problem in nonhomogeneous agent systems in the presence of periodic energy‐limited denial‐of‐service ...(DoS) attacks with an event‐triggered control strategy. Under the developed framework, the proposed controller for different agents is composed of a dynamic compensator and a regulator, where the dynamic compensator on the first layer can copy the dynamics of the leader node. DoS attacks with a periodic (partially known) attack strategy are based on a time sequence and interrupt the data exchange over a shard network consisting of the leader node and dynamic compensators in the first layer. An event‐triggered control protocol is proposed to reduce the update frequency of the controller, and it also ensures that the output of every dynamic compensator can track the output of the leader node without occurring “Zeno phenomenon.” Based on the output regulator theory, the regulator for every agent can guarantee that all nonhomogeneous agents can converge to the trajectory of every dynamic compensator in the bottom layer. Finally, a simulation example is demonstrated to verify the new design method developed.
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For decreasing communication load and overcoming network constrains, such as the limited bandwidth and data loss in multi-agent networks, this paper integrates the two control strategies to ...investigate the bounded consensus problem of multi-agent systems (MASs) with external disturbance on the basis of an undirected graph, namely, the quantized control and the event-triggered control. In the existence of the external disturbance, two types of the high-gain control laws with the uniform quantized relative state measurements for the bounded consensus problem of MASs are first discussed, respectively. Then, in order to save the limited network resources in a multi-agent network, the event-triggered quantized communication protocols are designed based on the first case to obtain the bounded consensus in multi-agent systems. Moreover, it is shown that "Zeno behavior" phenomenon can be excluded under the two event-triggered quantized control mechanisms, and the boundness of the relative state error can be adjusted by selecting the different parameters. Finally, two examples are shown to validate the feasibility and efficiency of our theoretical analysis.
In this article, a distributed observer- and event-based practical consensus control for networked systems subject to adaptive nonlinear couplings is investigated. Considering that the node's state ...is not always measurable and the finite communication bandwidth exists in engineering systems, two distributed adaptive event-triggered control protocols subject to nonlinear couplings are proposed under observer-based dynamic output feedback. Then, distributed dynamic event-triggered control policies corresponding to two abovementioned adaptive controllers are proposed, respectively. The proposed nonlinear coupled event-triggered control schemes not only overcome continuous communication among nodes, but also relax the requirement of relying on global information for achieving a distributed practical consensus. Finally, the theoretical analysis is verified through a team of practical networked ground vehicles implemented through MATLAB/Simulink and robot operating systems environment.
Exploring novel multifunctional rare earth materials is very important because these materials have fundamental interests, such as new structural facts and connecting modes, as well as potential ...technological applications, including optics, magnetic properties, sorption, and catalytic behaviors. Especially, employing these nanomaterials for sensing or catalytic reactions is still very challenging. Herein, a new superstable, anionic terbium‐metal–organic‐framework, H2N(CH3)2Tb(cppa)2(H2O)2, (China Three Gorges University (CTGU‐1), H2cppa = 5‐(4‐carboxyphenyl)picolinic acid), is successfully prepared, which can be used as a turn‐on, highly‐sensitive fluorescent sensor to detect Eu3+ and Dy3+, with a detection limitation of 5 × 10−8 and 1 × 10−4m in dimethylformamide, respectively. This result represents the first example of lanthanide‐metal–organic‐frameworks (Ln‐MOF) that can be employed as a discriminative fluorescent probe to recognize Eu3+ and Dy3+. In addition, through ion exchanging at room temperature, Ag(I) can be readily reduced in situ and embedded in the anionic framework, which leads to the formation of nanometal‐particle@Ln‐MOF composite with uniform size and distribution. The as‐prepared Ag@CTGU‐1 shows remarkable catalytic performance to reduce 4‐nitrophenol, with a reduction rate constant κ as large as 2.57 × 10−2 s−1; almost the highest value among all reported noble‐metal‐nanoparticle@MOF composites.
A new porous, anionic Tb‐metal–organic‐framework, China Three Gorges University (CTGU‐1), can serve as a turn‐on sensor for detection of Eu3+ and Dy3+, with different detection limits. Additionally, spontaneous in situ reduction and immobilization of ion‐exchanged Ag(I) to Ag nanoparticles in the anionic framework result in an Ag@CTGU‐1 composite, which can remarkably catalyze the reduction of 4‐nitrophenol.
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Interfacial engineering is an appealing strategy to construct heterogeneous nanostructures and tunes the morphology of metal–organic frameworks (MOFs) and MXenes for hybrid supercapacitors. Herein, a ...temperature-controlled annealing process is introduced to fabricate Ni-MOFs/V2CTx–MXene (Tx denotes the surface groups, –O, –OH, and –F) composites on Ni foam (NF) (namely MOF/MXene/NF) and subsequently build the heterogeneous structure of a hierarchically-porous nanorod composite without a change in the crystalline structure. Experimental characterizations and theoretical calculations reveal that Ni–O–V bridging bonds are constructed at the Ni-MOF and V2CTx interfaces, which could be used to establish a favorable electronic structure in promoting conductivity and reactivity. The optimized MOF/MXene/NF electrode obtained at 300 °C (i.e., MOF/MXene/NF-300) delivers an ultrahigh specific capacity of 1103.9 C g−1 at 1 A g−1. The as-assembled hybrid supercapacitor, composed of MOF/MXene/NF-300 as the cathode and activated carbon/NF as the anode, delivers a high energy density of 46.3 W h kg−1 at a power density of 746.8 W kg−1 and an outstanding cycling stability of ca. 118.1% capacity retention after 15 000 cycles. Such an achievement stems from the strong chemical bonds at the interface and unique porous morphology. This work suggests a new avenue for designing and preparing robust and high-performance electrode materials for hybrid supercapacitors.
The rapid detection of antibiotics and organic explosives has gradually garnered great attention, due to concerns about sustainability and the environment. In this work, a luminescent Tb-based metal ...organic gel (MOG(Tb) gel) was prepared by Al-based MOG induced in situ replacement of Al 3+ with Tb 3+ . Remarkably, the strong emission of the post-synthesized MOG(Tb) xerogel can be quenched efficiently by using trace amounts of sulfamethazine (SMZ) and sulfadiazine (SDZ) even in the presence of other competing antibiotics. Furthermore, the MOG(Tb) xerogel has shown its application as a chemosensor for the highly selective detection of nitroaromatics such as 2,4-dinitrophenol (2,4-DNT) and 2,6-dinitrophenol (2,6-DNT). To further verify the recyclability of MOG(Tb), detection experiments were carried out with recovered xerogel to give a satisfactory result.
Designing efficient multifunctional electrocatalysts for water and urea splitting to produce green hydrogen presents a significant yet worthwhile challenge. Herein, the morphology and electronic ...structure of cobalt metaphosphate (Co2P4O12) by vanadium (V) doping, resulting in improved electrocatalytic activity and stability for hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and urea oxidation reaction (UOR) are simultaneously regulated. Theory calculations show that V‐doped Co2P4O12 (V‐Co2P4O12) can boost the kinetics of catalytic reactions by optimizing the d‐band center of Co atoms and the binding strength of intermediates, as well as enhancing the density of states. Moreover, the doping of V into Co2P4O12 crystalline structure benefits the formation of a thicker amorphous layer during the catalytic process, which could enhance its alkaline corrosion resistance and stability. Additionally, the multilevel nanostructures of V‐Co2P4O12 provide rich active sites for catalytic reactions. As a result, a two‐electrode electrolyzer assembled by V‐doped Co2P4O12 delivers low voltages for overall water and urea splitting. The superior performance suggests that the proposed V‐doping strategy is a promising way to regulate electrocatalytic activity for catering to green electrocatalytic applications.
The morphology and electronic structure of the Co2P4O12 catalyst are simultaneously regulated by V doping, which endows the catalyst with enhanced hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and urea oxidation reaction (UOR) performance. Thanks to the excellent trifunctional catalytic performance, the assembled two‐electrode electrolyzers enable efficient overall water and urea splitting at low overpotentials.
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Designing novel multifunctional rare-earth metal-organic frameworks (MOFs) has attracted intensive attention. In particular, employing such materials for sensing or catalytic reactions is still very ...challenging. Here, a new 3D porous Eu(
iii
)-MOF, Eu(cppa)(OH)·
xS
(denoted as
CTGU-19
,
S
= solvent molecule, CTGU = China Three Gorges University), was synthesized by using 5-(4-carboxyphenyl)picolinic acid (H
2
cppa) as an organic ligand, and it shows a 3D (3,12)-connected topological net with the point symbol (4
20
·6
28
·8
18
)(4
3
)
4
, constructed from cubane-shaped tetranuclear europium building units. Interestingly,
CTGU-19
can be used as a highly sensitive luminescent sensor to identify ornidazole (ODZ) and nitrofurantoin (NFT) at different excitation wavelengths. This result represents the first example of a lanthanide-metal-organic-framework (Eu-MOF) that can be employed as a discriminating fluorescent probe to recognize ODZ and NFT at different excitation wavelengths. Furthermore, after loading
CTGU-19
with Ag and/or Au nanoparticles, the composites exhibit efficient catalytic performance for reducing 2-/3-/4-nitrophenols (2-/3-/4-NP), in which the unit mass reduction rate constants of Ag
0.8
Au
0.2
@
CTGU-19
for 2-NP, 3-NP, and 4-NP reach 68.8, 53.80, and 52.34 s
−1
g
−1
, respectively.
A new porous MOF,
Eu-MOF
, can serve as a turn-off sensor for detection of ornidazole /nitrofurantoin antibiotics at different excitation wavelength. Additionally, Ag
x
Au
1−
x
@
Eu-MOF
composite can remarkably catalyze the reduction of nitrophenol.
