Unique Catalytic Performance Research Articles

Hydroxylated TiO2-induced high-density Ni clusters for breaking the activity-selectivity trade-off of CO2 hydrogenation

The reverse water gas shift reaction can be considered as a promising route to mitigate global warming by converting CO2 into syngas in a large scale, while it is still challenging for non-Cu-based catalysts to break the trade-off between activity and selectivity. Here, the relatively high loading of Ni species is highly dispersed on hydroxylated TiO2 through the strong Ni and −OH interactions, thereby inducing the formation of rich and stable Ni clusters (~1 nm) on anatase TiO2 during the reverse water gas shift reaction. This Ni cluster/TiO2 catalyst shows a simultaneous high CO2 conversion and high CO selectivity. Comprehensive characterizations and theoretical calculations demonstrate Ni cluster/TiO2 interfacial sites with strong CO2 activation capacity and weak CO adsorption are responsible for its unique catalytic performances. This work disentangles the activity-selectivity trade-off of the reverse water gas shift reaction, and emphasizes the importance of metal−OH interactions on surface.

Substrate-Assisted Atomic Dispersion of Cobalt for Alkaline Water Electrolysis.

Atomically dispersed single-atom catalysts have recently attracted broad research interest due to their high atom efficiency and unique catalytic performance. In this study, atomic dispersion of cobalt is achieved using a chemical bath deposition method on a highly stable alkali titanate film (Ti/KTiO). These films were characterized using a variety of techniques, with atomic dispersion confirmed via grazing incidence X-ray absorption spectroscopy and ab initio modeling of single-atom systems. This modeling indicated that the alkali ion incorporated into the film facilitates atomic dispersion. Experimentally, the Ti/KTiO-supported Co(OH)2 catalysts exhibited remarkable electrochemical performance, with an overpotential of 163 mV to achieve a current density of 10 mA cm-2 with a catalyst loading of ∼0.1 mg cm-2 and high stability. These results show the potential of Ti/KTiO/Co(OH)2 catalysts for atomically efficient hydrogen production.

Remarkable enhancement of CO oxidation over Pt1/CeO2 catalysts by atomically dispersed tungsten

Ceria-supported atomically dispersed Pt is of great interest in CO oxidation due to their unique catalytic performance and high metal utilization. However, the intrinsic activity of the Pt1/CeO2 single atom catalysts may not be desirable due to the overstabilization of Pt2+ species in the CeO2 matrix. Herein, the local environment of Pt2+ species was tailored by introducing a tungsten oxide additive into the Pt1/CeO2 catalyst, achieving a dramatic improvement in catalytic performance for CO oxidation at low temperatures. The optimized catalyst with 2.5 wt% W loading achieved 100 % CO conversion at 150 °C, which was 120 °C lower than that of the unmodified Pt/CeO2 catalyst. Through in situ infrared spectroscopy and temperature-programmed reduction characterizations, as well as theoretical calculations, we concluded that the tungsten additive modulated the interactions between Pt2+ species and CeO2. Thus, the reducibility of Pt was enhanced, which facilitated the formation of catalytically active metallic Pt0 species during the reaction.

Efficient Electrocatalytic Ammonia Synthesis via Theoretical Screening of Titanate Nanosheet-Supported Single-Atom Catalysts.

The electrocatalytic nitrogen reduction reaction (NRR) for synthesizing ammonia holds promise as an alternative to the traditional high-energy-consuming Haber-Bosch method. Rational and accurate catalyst design is needed to overcome the challenge of activating N2 and to suppress the competitive hydrogen evolution reaction (HER). Single-atom catalysts have garnered widespread attention due to their 100% atom utilization efficiency and unique catalytic performance. In this context, we constructed theoretical models of metal single-atom catalysts supported on titanate nanosheets (M-TiNS). Initially, density functional theory (DFT) was employed to screen 12 single-atom catalysts for NRR- and HER-related barriers, leading to the identification of the theoretically optimal NRR catalyst, Ru-TiNS. Subsequently, experimental synthesis of the Ru-TiNS single-atom catalyst was successfully achieved, exhibiting excellent performance in catalyzing NRR, with the highest NH3 yield rate reaching 15.19 μmol mgcat-1 h-1 and a Faradaic efficiency (FE) of 15.3%. The combination of experimental results and theoretical calculations demonstrated the efficient catalytic ability of Ru sites, validating the effectiveness of the constructed theoretical screening process and providing a theoretical foundation for the design of efficient NRR catalysts.

Computational Insights into the Photoinduced Dimeric Gold-Catalyzed Divergent Dechloroalkylation of gem-Dichloroalkanes with Alkenes.

The employment of dinuclear Au(I) catalysts in photomediated modern organic transformations has attracted significant attention over the past decade, which commonly demonstrates unique catalytic performance compared with the corresponding mononuclear gold complexes. Nevertheless, detailed mechanisms of dinuclear gold catalysis remain ambiguous, and further mechanistic understanding is highly desirable. Herein, computational studies were carried out to gain mechanistic insights into the photoinduced dinuclear gold-catalyzed divergent dechloroalkylation of gem-dichloroalkanes. Computational results suggest that a proton transfer from the additive, Hantzsch ester (HE), to the base, guanidine, could lead to an ionic pair complex, which is ready to undergo excitation under blue light irradiation to result in the corresponding triplet excited state. Then, the excited complex might undergo oxidative quenching with the dinuclear gold photocatalyst [AuI-AuI]2+, via a single-electron-transfer (SET) step to afford an unusual [Au1/2-Au1/2]+ dinuclear species. The corresponding mononuclear gold catalyst, [AuI]+, however, is not ready to enable the analogous step to give a [Au0] species, which might account for the unique characteristics of dinuclear gold catalysis. Subsequently, the formed [Au1/2-Au1/2]+ intermediate could trigger a Cl-atom transfer from dichloromethane in an inner-sphere manner to furnish a critical chloromethyl radical. Next, the resulting chloromethyl radical could attack the alkenyl moiety of substrates to generate the corresponding alkyl radicals. Then, three possible mechanistic pathways were explored to rationalize the substrate-dependent divergent transformations in this protocol. The main factors responsible for the diversified transformations were discussed.

Emerging Strategies for Modifying Cytochrome P450 Monooxygenases into Peroxizymes.

ConspectusCytochrome P450 monooxygenase is a versatile oxidizing enzyme with great potential in synthetic chemistry and biology. However, the dependence of its catalytic function on the nicotinamide cofactor NAD(P)H and redox partner proteins limits the practical catalytic application of P450 in vitro. An alternative to expensive cofactors is low-cost H2O2, which can be used directly to exploit the catalytic potential of P450s. However, the peroxide shunt pathway is generally inefficient at driving P450 catalysis compared to normal NAD(P)H-dependent activity. Over the last few decades, the scientific community has made continuous efforts to use directed evolution or site-directed mutagenesis to modify P450 monooxygenases into their peroxizyme modes─peroxygenase and peroxidase. Despite significant progress, obtaining efficient P450 peroxizymes remains a huge challenge. Here, we summarize our efforts to modulate peroxizyme activity in P450 monooxygenases and exploit their catalytic applications in challenging selective C-H oxidation, oxygenation, and oxyfunctionalization over the past seven years. We first developed a dual-functional small molecule (DFSM) strategy for transforming P450BM3 monooxygenase into peroxygenase. In this strategy, the typical DFSM, such as N-(ω-imidazolyl)-hexanoyl-l-phenylalanine (Im-C6-Phe), binds to the P450BM3 protein with an anchoring group at one end and plays a general acid-base catalytic role in the activation of H2O2 with an imidazolyl group at the other end. Compared with the O-O homolysis mechanism in the absence of DFSM, the addition of DFSM efficiently enables the heterolytic O-O cleavage of the adduct Fe-O-OH, thus being favored for the formation of active species compound I, which has been demonstrated by combining crystallographic and theoretical calculations. Furthermore, protein engineering showed the unique catalytic performance of DFSM-facilitated P450 peroxygenase for the highly difficult selective oxidation of C-H bonds. This catalytic performance was demonstrated during the chemoselective hydroxylation of gaseous alkanes, regioselective O-demethylation of aryl ethers, highly (R)-enantioselective epoxidation of styrene, and regio- and enantiomerically diverse hydroxylation of alkylbenzenes. Second, we demonstrated that DFSM-facilitated P450BM3 peroxygenase could be effectively switched to an efficient peroxidase mode through mechanism-guided protein engineering of redox-sensitive residues. Utilizing the peroxidase function of P450 enabled the direct nitration of unsaturated hydrocarbons including phenols, aromatic amines, and styrene derivatives, which was not only the P450-catalyzed direct nitration of phenols and aromatic amines for the first time but also the first example of the direct biological nitration of olefins. Finally, we report an H2O2 tunnel engineering strategy to enable peroxygenase activity in several different P450 monooxygenases for the first time, providing a general approach for accessing engineered P450 peroxygenases. In this Account, we highlight the emerging strategies we have developed for producing practical P450 peroxizyme biocatalysts. Although the DFSM strategy is primarily applied to P450BM3 to date, both strategies of redox-sensitive residue engineering and H2O2 tunnel engineering show great potential to extend to other P450s. These strategies have expanded the scope of applications of P450 chemistry and catalysis. Additionally, they provide a unique solution to the challenging selective oxidation of inert C-H bonds in synthetic chemistry.

Superhydrophobic MOF/polymer composite with hierarchical porosity for boosting catalytic performance in an humid environment.

The poor hydrostability of most reported metal-organic frameworks (MOFs) has become a daunting challenge in their practical applications. Recently, MOFs combined with multifunctional polymers can act as a functional platform and exhibit unique catalytic performance; they can not only inherit the outstanding properties of the two components but also offer unique synergistic effects. Herein, an original porous polymer-confined strategy has been developed to prepare a superhydrophobic MOF composite to significantly enhance its moisture or water resistance. The selective nucleation and growth of MOF nanocrystals confined in the pore of PDVB-vim are closely related to the structure-directing and coordination-modulating properties of PDVB-vim. The resultant MOF/PDVB-vim composite not only produces superior superhydrophobicity without significantly disturbing the original features but also exhibits a novel catalytic activity in the Friedel-Crafts alkylation reaction of indoles with trans-β-nitrostyrene because of the accessible sites and synergistic effects.

Constructing Interconnected Hollow Mesopore Sn-Si Mixed Oxide Microspheres by Aerosol-Assisted Alkali Treatment with Enhanced Catalytic Performance in Baeyer-Villiger Oxidation

In this work, Sn-Si mixed oxide microspheres with concave hollow morphologies were first synthesized by a simple aerosol method using the very common commercial surfactant cetyl trimethyl ammonium bromide (CTAB) as a template, and then highly interconnected mesoporous and hollow Sn-Si mixed oxide microspheres were synthesized via an alkali (NaOH) treatment in the presence of CTAB. The results show that CTAB plays a crucial role not only in forming hollow morphologies during the aerosol process, but also protecting the amorphous framework and thus preventing the excessive loss of Sn species during the NaOH treatment. More importantly, it widens mesoporous distribution and forms interconnected mesoporous channels. The catalytic performance of Baeyer–Villiger oxidation on the interconnected mesoporous and hollow Sn-Si mixed oxide microspheres with 2-adamantanone and hydrogen peroxide was 9.4 times higher than that of the sample synthesized without the addition of CTAB; 2.3 times that of the untreated parent, which was due to the excellent diffusion properties derived from the hollow and interconnected mesopore structure. This method is mild, simple, low-cost, and can be continuously produced, which has the prospect of industrial application. Furthermore, the fundamentals of this study provide new insights for the rational design and preparation of highly interlinked mesoporous and hollow metal-oxides with unique catalytic performances.

Fabrication of Heterostructural FeNi3-Loaded Perovskite Catalysts by Rapid Plasma for Highly Efficient Photothermal Reverse Water Gas Shift Reaction.

Metal-semiconductor heterostructured catalysts have attracted great attention because of their unique interfacial characteristics and superior catalytic performance. Exsolution of nanoparticles is one of the effective and simple ways for in-situ growth of metal nanoparticles embedded in oxide surfaces and their favorable dispersion and stability. However, both high-temperature and a reducing atmosphere are required simultaneously in conventional exsolution, which is time-consuming and costly, and particles often agglomerate during the process. In this work, Ca0.9Ti0.8Ni0.1Fe0.1O3-δ (CTNF) is exposed to dielectric blocking discharge (DBD) plasma at room temperature to fabricate alloying FeNi3 nanoparticles from CTNF perovskite. FeNi3-CTNF has outstanding catalytic activity for photothermal reverse water gas shift reaction (RWGS). At 350°C under full-spectrum irradiation, the carbon monoxide (CO) yield of FeNi3-CTNF (10.78mmol g-1 h-1) is 11 times that of pure CaTiO3(CTO), and the CO selectivity is 98.9%. This superior catalytic activity is attributed to the narrow band gap, photogenerated electron migration to alloy particles, and abundant surface oxygen vacancies. The carbene pathway reaction is also investigated through in-situ Raman spectroscopy. The present work presents a straightforward method for the exsolution of nanoalloys in metal-semiconductor heterostructures for photothermal CO2 reduction.

Tuning Redistribution of CuOx Nanoparticles on TiO2 Support.

Nanoparticles exhibit unique catalytic performance, depending on their nanoscale size. However, controlling the particle size of the supported catalysts is still challenging. Here, we present a method for tunable redistribution of CuOx nanoparticles on rutile TiO2 support by physically adding pristine TiO2. The redistribution is driven by the work function difference (WFD) between the TiO2 support and the TiO2 additive, both of which exhibit distinct values, as determined through Kelvin probe force microscopy and electron binding energy analysis. Addition of TiO2 with lower work function (rutile) promotes electron transfer toward the CuOx/TiO2 composite, resulting in nanoparticle aggregation, while addition of TiO2 with higher work function (anatase) results in smaller CuOx on TiO2. The increase in particle size and electron density of CuOx, driven by the addition of rutile TiO2, promoted the complete conversion of nitrobenzene (100%) within 5 h. This is 2.7 times that of dispersed and degraded CuOx driven by mixing with anatase TiO2 (36.9%).

Catalytic Properties of Nanometric Metal Overlayers with Two‐Dimensional Structures

AbstractAlthough most of the currently used solid catalysts possess a three‐dimensional structure of nanoparticles dispersed on a porous support, the nanoparticle structure should not be considered the optimal structure for all catalytic reactions due to some disadvantages such as thermal instability and catalyst poisoning. Herein, we present the unique catalytic performance of a two‐dimensional metal foil‐supported nanometric Rh thin film, referred to as the “Rh overlayer”, for a catalytic CO−NO reaction and a stoichiometric three‐way catalytic reaction under practical conditions. The extremely high turnover frequency for NO reduction using two‐dimensional Rh is a key to understanding this phenomenon, the detailed mechanism of which can be explained by theoretical calculations.

Single‐atom catalysts for the electrochemical reduction of carbon dioxide into hydrocarbons and oxygenates

AbstractThe electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries. In this technology, an electrocatalytic material and renewable energy‐generated electricity drive the conversion of carbon dioxide into high‐value chemicals and carbon‐neutral fuels. Over the past few years, single‐atom catalysts have been intensively studied as they could provide near‐unity atom utilization and unique catalytic performance. Single‐atom catalysts have become one of the state‐of‐the‐art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide. However, it remains a challenge for single‐atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide. In this review, we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single‐atom catalysts. It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through single‐atom catalysts so that it can be a guide for future research and development on catalysts with industry‐ready performance for the electrochemical reduction of carbon dioxide into high‐value chemicals and carbon‐neutral fuels.

Single‐Atom Fe Catalyst for Catalytic Ethane Dehydrogenation to Ethylene

AbstractThe single atom catalysts (SACs) show unique catalytic performance in heterogeneous reactions owing to unsaturated coordination sites and high metal atom dispersion. Herein, a simple wet impregnation method was utilized to synthetize of Fe−Al2O3 catalysts. The Fourier transformation infrared spectroscopy (FTIR) revealed that abundant OH group attached to the support (Al2O3) surface facilitating formation of isolated Fe single atom. High resolution transmission electron microscope (HR‐TEM) and extended X‐ray absorption fine structure (EXAFS) confirmed the Fe single atom architecture. Fe−Al2O3 (4.5 wt %) performed enhanced stability and activity on ethane dehydrogenation reaction.

Three-dimensional graphene anchored nZVI hybrid MnO2 as a dissolved oxygen activated Fenton-like catalyst for efficient mineralization of oxytetracycline

This work is dedicated to achieving the high mineralization efficiency of oxytetracycline (OTC) in a dissolved oxygen (DO) activated Fenton-like system by constructing a catalyst with unique catalytic performance. Three-dimensional graphene anchored nZVI hybrid MnO2 (3D-rGO@nZVI/MnO2) with layered and porous structures was synthesized and characterized by field emission scanning electron microscopy coupled with an energy dispersive spectrometer (SEM-EDS), Brunner-Emmet-Teller (BET) analysis, X-ray diffraction (XRD) measurement and Raman spectroscopy. The experimental results showed that the removal efficiency of OTC could reach 100.0% with outstanding TOC decrease of 84.0% at natural pH in the 3D-rGO@nZVI/MnO2-DO system. Moreover, negligible harmful intermediates were detected by ultra-performance liquid chromatography-mass spectrometry (UPLC-MS) after the reaction in the 3D-rGO@nZVI/MnO2-DO system. Reactive oxygen species (ROSs) detection, electrochemical measurements and X-ray photoelectron spectroscopy (XPS) analysis confirmed that the elimination mechanism of OTC was the unique catalytic degradation caused by the synergism of •OH and 1O2. The unprecedented synchronous generation of •OH and 1O2 by DO activation provides an innovative strategy for further exploration of Fenton-like system toward more effective degradation of organic pollutants.

Theoretical exploration of Rh1/CeO2 catalysts with high performance using CO oxidation as a probe reaction

Rh1/CeO2 attracts much attention in single-atom catalysis due to its unique catalytic performance and maximum atomic efficiency. Since different possible structures of Rh1/CeO2 coexist in real catalysts, it is hard to discriminate their catalytic roles and reaction mechanism due to the difficulty of preparing pure modeling catalyst. To solve this difficult problem, the adsorption and reaction behaviors of CO and O2 on four modeling catalysts of Rh1/CeO2 were systematically investigated by using density functional theory calculation in this work. The catalytic role and CO oxidation mechanism on Rh1/CeO2 catalysts were elucidated. On Rh1/CeO2(111), CO reacts with adsorbed O2 via Eley-Rideal mechanism; and the rate-determined step of CO oxidation cycle is CO reaction with the rest O atom of O2 with a barrier of 0.99 eV. On Rh1/CeO2-δ(111), CO reacts with activated O2 via Langmuir-Hinshelwood mechanism and continue the oxidation cycle via Rh1/CeO2(111). On RhxCe1-xO2, CO directly reacts with surface oxygen without barrier to form RhxCe1-xO2-δ; while the barrier of CO oxidation cycle on RhxCe1-xO2-δ is 1.18 eV. Upon the discrimination of the catalytic roles of Rh1/CeO2 catalysts with different structures, several important insights into design and development of Rh1/CeO2 catalysts with high oxidation performance were proposed.

Intermetallic-driven highly reversible electrocatalysis in Li–CO2 battery over nanoporous Ni3Al/Ni heterostructure

Li–CO2 batteries, which integrate CO2 utilization and electrochemical energy storage, offer the prospect of utilizing a greenhouse gas and providing an alternative to the well-established lithium-ion batteries. However, they still suffer from rather limited reversibility, low energy efficiency, and sluggish CO2 redox reaction kinetics. To address these key issues, a nanoporous Ni3Al intermetallic/Ni heterojunction (NP–Ni3Al/Ni) is purposely engineered here via an alloying–etching protocol, whereby the unique interactions between Al and Ni in Ni3Al endow NP-Ni3Al/Ni with optimum reactant/product adsorption and thus unique catalytic performance for the CO2 redox reaction. Furthermore, the nanoporous spongy structure benefits mass transport as well as discharge product storage and enables a rich multiphase reaction interface. In situ Raman studies and theoretical simulations reveal that both CO2 reduction and the co-decomposition of Li2CO3 and C are distinctly promoted by NP-Ni3Al/Ni, thereby greatly improving catalytic activity and stability. NP-Ni3Al/Ni offers promising application potential in Li–CO2 batteries, with its scalable fabrication, low production cost, and superior catalytic performance.

Copper-catalyzed amination of arene

<p indent="0mm">Aromatic amines are widely used in the fields of natural products, pharmaceutical chemistry and materials science, thus the new methods of metal-catalyzed C–N bond coupling for constructing aromatic amines always have always been the focus of attention of chemists and the scientific community. Copper, as a catalyst for the amination of arenes, has attracted extensive attention due to its unique catalytic performance and variety of oxidation states. In this review, the recent progress in the construction of aromatic compounds C(sp²)–N catalyzed by copper is reviewed, and the reaction mechanisms of representative amination reactions are briefly described.

Generation of sub-5 nm AuNPs in the special space of the loop-cluster corona of a polymer vesicle: preparation and its unique catalytic performance in the reduction of 4-nitrophenol.

The hybrid vesicle AuNP@LCCV, in which a large number of AuNPs with an average size of about 2.8 nm were densely and uniformly distributed in an isolated state throughout the corona of the unusual polymer vesicle, was prepared via in situ reduction of Au3+ ions, which were encapsulated in advance in the unique polymer vesicle (LCCV) consisting of a hydrophobic membrane of poly(2-phenyl-2-oxazoline) and a hydrophilic loop-cluster corona of polyethyleneimine. The vesicle was formed via self-assembly from a comb-like block copolymer in which a polystyrenic main chain was grafted densely with diblock polyethyleneimine-b-poly(2-phenyl-2-oxazoline) and acted as a reactor for the reduction of Au3+. The hybrid vesicle AuNP@LCCV showed powerful catalytic ability in the reduction of nitrophenols (NPs). Interestingly, the reduction reactions of NPs showed a remarkably long induction time, which could be shortened dramatically from 60 min to 1-2 min by greatly increasing the concentration of NaBH4. It is revealed that the oxygen adsorbed on the AuNPs significantly inhibited the reduction, causing the induction time. Once the oxygen is chemically cleaned from the surface of the AuNPs, the reduction of 4-NP proceeds gradually for a while and then completes suddenly. The reduction mechanism accompanying the oxygen-dependent induction time is proposed from the view of the strong oxygen affinity of the catalyst AuNP@LCCV.

Emerging dual-atomic-site catalysts for electrocatalytic CO2 reduction

The electrochemical CO2 reduction reaction (CO2RR) to yield high-value added fuels and chemicals provides a promising approach towards global carbon neutrality. Constant endeavors have been devoted to the exploration of high-efficiency catalyst with rapid reaction kinetics, low energy input, and high selectivity. In addition to the maximum metal atomic utilization and unique catalytic performance of single-atom catalyst (SAC), dual-atomic-site catalysts (DASCs) offer more sophisticated and tunable atomic structure through the modulations of another adjacent metal atom, which can bring new opportunities for CO2RR as a deeper extension of SACs and have recently aroused surging interest. In this review, we highlight the recent advances on DASCs for enhancing CO2RR. First, the classification, synthesis, and identification of DASCs are provided according to the geometric structure and electronic configuration of dual-atomic active sites. Then, the catalytic applications of DASCs in CO2RR are categorized based on marriage-type, hetero-nuclear, and homo-nuclear dual-atomic sites. Particularly, the structure-activity relationship of DASCs in CO2RR is elaborately summarized through systematically analyzing the reaction pathways and the atom structures. Finally, the opportunities and challenges are proposed for inspiring the design of future DASCs with high structural accuracy and high CO2RR activity and selectivity.

Fully Exposed Metal Clusters: Fabrication and Application in Alkane Dehydrogenation

Alkanes are the foremost basic energy sources and represent an important basic chemical material for industrial applications. Highly efficient activation of C–H bonds can convert abundant alkanes into value-added products, such as alkenes and their corresponding polymers. Therefore, C–H bond activation of alkanes has attracted widespread attention in heterogeneous catalysis. Fully exposed cluster catalysts (FECCs), as a bridge linking metal single atoms (SAs) and nanoparticles (NPs), have been widely studied for many catalytic reactions, especially for alkane dehydrogenation. On FECCs, the highly exposed active sites with multiple metal atoms can promote adsorption of alkanes and intermediates, thus enabling facile C–H activation. Moreover, the electron-rich surface can facilitate the desorption of products to suppress overdehydrogenation and coke formation. Therefore, FECCs have exhibited remarkable catalytic performance in alkane dehydrogenation, compared with SAs and NPs. In this Review, we highlight the developments on FECCs, including the structure design and their unique catalytic performance in dehydrogenation of alkanes. The synthetic methods to fabricate FECCs are discussed for alkane dehydrogenation. Subsequently, recent progresses on understanding the relationship between catalytic performance and geometric/electronic structure of FECCs are summarized, to provide the insights into the nature of structure dependence and metal dependence in alkane dehydrogenation. The strategies to stabilize FECCs for alkane dehydrogenation, including support confining and bimetallic system construction, are systematically reviewed to provide a useful guidance for the catalyst design. Lastly, major prospects in FECCs are illustrated from the viewpoint of alkane dehydrogenation.