Multifunctional Catalysts Research Articles

Construction of multifunctional interface engineering on Cu‐SSZ‐13@Ce‐MnOx/Mesoporous-silica catalyst for boosting activity, SO2 tolerance and hydrothermal stability

Although small pore Cu-SSZ-13 catalysts have been successful as commercial catalysts for controlling NOx emissions from mobile sources, the challenges of high light-off temperature, SO2 tolerance and hydrothermal stability still need to be addressed. Here, we synthesized a multifunctional core-shell catalyst with Cu-SSZ-13 as the core phase and Ce-MnOx supported Mesoporous-silica (Meso-SiO2) as the shell phase via self-assembly and impregnation. The core-shell catalyst exhibited excellent low-temperature activity, SO2 tolerance and hydrothermal stability compared to the Cu-SSZ-13. The Ce-MnOx species dispersed in the shell are found to enhance both the acidic and oxidative properties of the core-shell catalyst. More critically, these species can rapidly activate NO and oxidize it to NO2, which allows the NH3-SCR reaction on the core-shell catalyst to be initiated in the shell phase. Meanwhile, Ce-MnOx species can react preferentially with SO2 as sacrifice components, effectively avoiding the sulfur inactivation of the copper active sites. Furthermore, the hydrophobic Meso-SiO2 shell provides an important barrier for the core phase, which reduces the loss of active species, acid sites and framework Al of the aged core-shell catalyst and mitigates the collapse of the zeolite framework. This work provides a new strategy for the design of novel and efficient NH3-SCR catalysts.

DFT and machine learning studies on a multi-functional single-atom catalyst for enhanced oxygen and hydrogen evolution as well as CO2 reduction reactions

In this contribution, the design of a graphene-supported high-entropy single-atom catalyst (HESAC) composed of Fe, Co, Ni, and Ru metal atoms (FeCoNiRu-HESAC) is proposed. Negative formation energy and positive dissociation potentials indicate such materials' thermodynamic and electrochemical stability. Based on density functional theory (DFT) calculations, Co active sites lead to the overpotentials of 0.28 VRHE for oxygen evolution reaction (OER), 0.16 VRHE for hydrogen evolution reaction (HER), and 0.25 VRHE for CO2 reduction reaction (CO2RR) towards CO formation. These surpass the activity of CoN4 single-atom catalyst. More interestingly, the low CO2RR and HER overpotentials enable the FeCoNiRu-HESAC to produce syngas (CO + H2). In addition, the Fe, Ni, and Ru sites simply serve as counterparts to modify the performance of Co active sites through non-bonding interactions. Besides, machine learning (ML) implies that, the valence electrons of intermediates as well as the d orbital electrons of metal sites are the most important parameters affecting the reaction intermediates’ Gibbs free energy. According to these DFT and ML results, a strategy to design multifunctional HESACs electrocatalysts is developed.

P-Diarylboryl Halothiophenols as Multifunctional Catalysts via Photoactive Intramolecular Frustrated Lewis Pairs.

p-Diarylboryl halothiophenols are developed and unequivocally characterized. Their photophysical properties and catalytic performance are unveiled by experimental and theoretical investigations. This novel class of triarylboranes behaves as a Brønsted acid to generate the corresponding borylthiophenolate that can absorb visible light to undergo intramolecular charge transfer to form a radical pair consisting of a boron radical anion and thiyl radical, which acts as a single-electron reductant while engaging in hydrogen atom transfer to regenerate the parent borylthiophenol. The synthetic relevance of this mode of action is demonstrated by the establishment of unique catalysis that integrates three different yet tunable functions in a single catalytic cycle, thereby allowing borylthiophenols to solely promote the assembly of sterically congested 1,2-diols and 1,2-aminoalcohol derivatives via radical-radical cross-coupling.

Hierarchical metal–organic framework nanoarchitectures for catalysis

Metal–organic frameworks (MOFs) have garnered significant attention in the field of catalysis due to their unique advantages such as diverse coordination geometry, variable metal nodes, and organic linkers, facilitating precise structural and compositional control for achieving programmable catalytic functionalities. Although their inherent microporous structure could provide excellent shape selectivity during catalysis, it typically impedes the mass transfer process, thereby reducing the use of internal active sites and overall catalytic efficiency. Additionally, employing single MOFs as catalysts presents challenges in achieving complex catalytic reactions that require multifunctional active sites. In recent years, considerable research efforts have focused on designing and constructing hierarchical nanostructured MOFs to alleviate substrate diffusion limitations by introducing secondary nanopores, shortening diffusion distances via the construction of low-dimensional nanoarchitectures, and constructing multifunctional catalysts by integrating distinct MOFs with suitable functions. This review provides a comprehensive overview of the design, synthesis methods, and formation mechanisms of MOF-based hierarchical nanostructures in recent years. Subsequently, it further highlights their applications in thermal catalysis, electrocatalysis, and photocatalysis, along with the relationship between their hierarchical nanostructures and catalytic performances. Finally, it provides an outlook on the challenges and potential development directions of hierarchically structured MOF nanocatalysts.

An efficient multifunctional SnS2/g-C3N4 hierarchical nanoflower catalyst for electrocatalytic and photocatalytic applications

The rising energy demand via renewable sources and existence of organic pollutants in water has attracted the world-wide attention to attain sustainable ecosystems. The development of a multi-functional catalyst with significant economic and environmental implications remains a challenge. Herein, we synthesized SnS2/g-C3N4 hierarchical nanoflower using solvothermal method, verified by XRD and FTIR investigations. The surface morphology was analyzed using FESEM, TEM and HRTEM while optical absorption via UV–Vis spectroscopy. SnS2/g-C3N4 displayed outstanding electrocatalytic activity for HER and OER with smaller tafel slope and higher values of current density. The results are in accordance with Cdl and ECSA values, ensuing more active sites and surface area for a catalytic reaction to take place. As-prepared SnS2/g-C3N4 also exhibited 90 % photocatalytic MB deterioration in 90 min upon solar irradiation, following first order kinetics. Type-II mechanism for charge transfer alongwith reactive specie trapping experiment and cyclic stability is also presented. The findings suggests that SnS2/g-C3N4 emerged as proficient catalyst for electrocatalytic and photocatalytic applications.

Ultra-Small High-Entropy Alloy as Multi-Functional Catalyst for Ammonia Based Fuel Cells.

Ammonia fuel cells using carbon-neutral ammonia as fuel are regarded as a fast, furious, and flexible next-generation carbon-free energy conversion technology, but it is limited by the kinetically sluggish ammonia oxidation reaction (AOR), oxygen reduction reaction (ORR), and hydrogen evolution reaction (HER). Platinum can efficiently drive these three types of reactions, but its scale-up application is limited by its susceptibility to poisoning and high cost. In order to reduce the cost and alleviate poisoning, incorporating Pt with various metals proves to be an efficient and feasible strategy. Herein, PtFeCoNiIr/C trifunctional high-entropy alloy (HEA) catalysts are prepared with uniform mixing and ultra-small size of 2 ± 0.5nm by Joule heating method. PtFeCoNiIr/C exhibits efficient performance in AOR (Jpeak = 139.8 A g-1 PGM), ORR (E1/2 = 0.87V), and HER (E10 = 20.3 mV), outperforming the benchmark Pt/C, and no loss in HER performance at 100mA cm-2 for 200 h. The almost unchanged E1/2 in the anti-poisoning test indicates its promising application in real fuel cells powered by ammonia. This work opens up a new path for the development of multi-functional electrocatalysts and also makes a big leap toward the exploration of cost-effective device configurations for novel fuel cells.

Triazine-based covalent organic framework/ g-C3N4 heterojunction toward highly efficient photoactivation of peroxydisulfate for sulfonamides degradation

Rational design of multifunctional catalysts to realize the synergistic combination of photocatalysis and peroxydisulfate (PDS) activation process is a promising approach for the effective removal of recalcitrant pollutants. Herein, metal-free covalent organic framework/g-C3N4 (COF/CN) van der Waals heterojunction was synthesized by the in-situ polymerization on g-C3N4. The van der Waals force and π-π conjugation effect contributes to promoting the interfacial migration and separation of photoinduced carries. The photocatalytic removal efficiency of sulfamethazine (SMT) by COF/CN was increased by 4.9 and 6.6-folds compared to those of COF and g-C3N4, respectively. In the optimal COF/CN-3/PDS/Vis process, SO4•− and 1O2 were identified as the major contributors to SMT degradation. The relationship between the molecular reactivity of sulfonamides (SAs) and reaction kinetics was elucidated by density functional theory (DFT) calculations at the electron level. The degradation rates and pathways depend on the electronic distribution and reactive sites of SAs with five- or six-membered heterocyclic ring substituents. The nonradical attack on the aniline and the breakage of C-N bond were the common traits of SAs degradation, whereas a unique Smiles-type pathway occurred in SAs with six-membered heterocyclic substituents. This work expected to promote the insight for the interaction between molecular structures of pollutants and reactive species in wastewater purification.

Enhanced photoelectrochemical water splitting and photocatalytic decomposition performance of visible light active MgMnO3 perovskite nanostructure

Clean energy production and environmental remediation are imperative for sustainable future. Specially, exploration of multifunctional catalyst, for production of low-cost and eco-friendly hydrogen (H2) fuel as well as efficient decomposition of emerging pollutants are certainly needed. This study investigates magnesium manganese oxide (MgMnO3), a perovskite oxide, synthesized by simple citrate sol–gel technique, and its structural, morphological, optical, and photoelectrochemical properties were analyzed for the photodegradation of ciprofloxacin (CIP) antibiotic, methylene blue (MB) dye, and photoelectrochemical (PEC) water splitting. The cubic spinel crystal structure of MgMnO3 was confirmed through powder X-ray diffraction (XRD) analysis. FE-SEM images of the MgMnO3 material revealed a cauliflower-like morphology, consisting of an assembly of microspherical grains of varying sizes. UV–Vis spectroscopy exhibited broad absorption in the UV–Visible region, and the Tauc plot estimated a band gap of 1.54 eV. The MgMnO3 catalyst showed 88% and 96% for photodecomposition of CIP (10 mg/L) and MB (10 mg/L), respectively, using 35 mg and 30 mg of catalyst quantity over 90 min. In addition, MgMnO3 photoelectrode showcases superior photoelectrochemical behavior, exhibiting maximal photocurrent density of 13.21 mA cm−2 measured at 1.2 V vs. RHE and achieving a solar-to-hydrogen conversion efficiency of 2.45% compared to MgO and MnO2 photoelectrode. EIS measurements of MgMnO3 show enhanced charge transfer and recombination kinetics. Notably, the MgMnO3 electrode reveals outstanding photoelectrochemical durability, maintaining its stability even after continuous illumination for 9 h. Improved PEC properties could be attributed to wider light absorption, enhanced photo-induced charge-separations, and electron mobility. Thus, present study established an efficient and enduring multifunctional catalyst, catering photocatalytic degradation and PEC H2 generation.

Boosting low temperature CO2 methanation by tailoring Co species of CoAlO catalysts

The development of low-temperature CO2 methanation catalysts with excellent performance has been challenging. Herein, we report a CoAlO catalyst derived from layered double hydroxide (LDH) that modulates the Co species of a multifunctional catalyst through a reduction process. The CoAlO catalyst with a surface-coated CoO film achieved CO2 conversion up to 29.0 % at 160 °C, which was superior to that of noble metal catalysts. The multiple characterizations were used to reveal the relationship between the catalytic activity and the chemical state of Co species. The results showed that the reaction followed the H-assisted activation pathway, where the rate of formate intermediates generation determined the overall reactivity. Meanwhile, the reduction–oxidation (RO) process in the catalyst preparation and the water generated in the reaction could reduce the size of Co particles, which were favorable for CO2 activation. This work offers a promising catalyst design for low-temperature methanation reaction.

Oxygen-vacancy-rich Ru nanoclusters doped NiCo metal-organic framework for driving overall water electrolysis and supercapacitors

Due to the growing demand for clean renewable hydrogen fuel, the rational design of electrode materials' composition and structure holds significant importance in achieving efficient energy storage and conversion in electrochemical energy devices. In this study, we synthesize NiCo-MOF74/NF substrate using a one-step hydrothermal method, after which we successfully deposit a layer of Ru metal nanoclusters on the substrate by electrodeposition. Ru NCs@NiCo-MOF74/NF exhibits an exceptionally large specific surface area and excellent interface effects, demonstrating outstanding performance in both overall water splitting and supercapacitor applications. In a 1 M KOH alkaline solution, the device requires only 1.47 V output voltage to deliver a current density of 10 mA cm−2 for overall water splitting. As a supercapacitor, the unique nanoflower structure of Ru NCs@NiCo-MOF74/NF enables fast and reversible Faradaic reactions, providing high specific capacitance and rate performance. It shows a high areal capacitance of 1.664 mAh cm−2 at 1 mA cm−2, indicating excellent charge storage capacity. Assembled into an asymmetric supercapacitor (ASC) with Ru NCs@NiCo-MOF74/NF as the positive electrode, the device achieves a high energy density of 511.88 μWh cm−2 at a power density of 545.68 μW cm−2. After 5000 cycles, the capacitance retention rate is approximately 100 %, demonstrating remarkable cycling stability. This paves the way for the synthesis of multifunctional catalysts, opening up new possibilities in the field.

Aquivion-Based Spray Freeze-Dried Composite Materials for the Cascade Production of γ-Valerolactone.

The development of multifunctional catalysts is a necessary step to effectively carry out one-pot cascade reactions, such as that from furfural to γ-valerolactone. This research effort faces the challenge posed by the intrinsic limit of how many kinds of catalytic sites a single material can bear. In this work, the application of Spray-Freeze Drying (SFD) as a synthetic technique for the preparation of a wide range of innovative composite multi-functional catalysts is reported. Herein we show that by the proper combination of Aquivion as a highly active Brønsted acid catalyst and metal oxides as both support materials and Lewis acids (LAS) enable to achieve highly unique efficient and effective dual acid composite catalysts that are able to carry out the cascade reaction from furfural to γ-valerolactone. The dual catalytic system comprised of Aq/ZrO2 with 30 % polymer content prepared via spray-freeze drying exhibited GVL yields of 25 % after only 2 h at 180 °C and a remarkably high productivity of 4470 μmolGVL gCat -1 h-1, one of the highest reported results. Mechanistic studies based on experimental and advanced characterisation and spectroscopic techniques, such as, SEM, TEM, 15N MAS NMR and 19F MAS NMR indicate that activity arises from the proper tuning of BAS/LAS (Brønsted Acid Site/Lewis Acid Site) acidic properties.

Insights Into the one‐Step Dimethyl Ether Carbonylation to Ethanol Over Cu/ZnO@Cu‐MOR Core‐Shell Catalysts with Porogen Engagement

AbstractThis study investigates the one‐step ethanol synthesis from dimethyl ether and syngas using the catalysts combining Cu/ZnO oxides and modified Cu‐MOR zeolite. In addition to physically mixed two‐component catalysts, multifunctional catalysts featuring a Cu/ZnO core and modified zeolite (Cu‐MOR and HMOR) shell are also presented. Further, the porogenic agent of dihexadecyldimethylammonium bromide (DHAB) was involved in the synthesis process of the MOR zeolite components of Cu/ZnO@Cu‐MOR and Cu/ZnO/Cu‐MOR catalysts, but not in that of Cu/ZnO@Cu‐MOR° catalyst. A series of characterization measures including XRD, TGA, BET, SEM, TEM and EDS have been systematically studied on the prepared catalysts. Characterizations of the catalyst surface structure and texturing parameters revealed a disturbance in crystallinity upon Cu insertion, facilitating syngas separation and promoting DME carbonylation while preventing undesired CO hydrogenation. The addition of DHAB as a porogen in the synthesis of zeolite shell improved specific surface area and porosity of zeolite shell, and reduced coke deposition, without leaching active metal components, resulting in enhanced reaction properties. Cu/ZnO@Cu‐MOR core‐shell catalyst showed good performance with 28.9 % DME conversion and 43.8 % selectivity for ethanol. The optimized pore structure and enhanced catalytic performance of the modification process validate the effectiveness and efficiency of this strategy.

Catalytic co-pyrolysis of woody biomass with polypropylene: Effects of Korean loess hybrid catalysts and pyrolysis temperatures

This paper describes an effort to improve the catalytic characteristics of Korean loess (KL) for the co-pyrolysis of biomass and polypropylene, resulting in a unique multifunctional catalyst. Korean loess was physically and chemically transformed into a microporous structure (ZSM) fitting for co-pyrolysis. Using the catalysts manufactured above, analytical co-pyrolysis was carried out using a Py-GC/MS system with pinewood sawdust and polypropylene mixed at a ratio of 1:1 (w/w). To investigate the impacts of the use of catalysts and the pyrolysis temperatures on the distribution of volatile pyrolytic products, the experiments were designed to mix 2- or 8-fold catalyst mass quantities with feedstock and pyrolyze at temperatures of 500 °C, 600 °C, and 700 °C. Compared to pure Korean loess, the catalytic activity of the optimal hybrid catalyst (0.2KL/ZSM) favored decarbonylation over dehydration, making it more effective than mesoporous ZSM. Pyrolytic products generated using the hybrid catalyst (0.2KL/ZSM) had a higher hydrogen concentration (9.8 wt%) than pyrolytic products produced using ZSM catalysts (6.5 wt%). Because of this, the pyrolytic products were expected to be more compatible as a fuel over 0.2KL/ZSM, with an HHV of 27.4 MJ/kg as opposed to 26.5 MJ/kg over ZSM. Zeolite framework catalysts could promote the production of aromatic chemicals (3.0 mg/g for non-catalyst, 34.7 mg/g for KL, and 53.9 mg/g for 0.2KL/ZSM) in the co-pyrolysis of PP with pine, which synergistically enhance oligomerization, cyclization, and aromatization reactions at catalyst acid sites. Concerning aromatic hydrocarbon yields, 0.2KL/ZSM could be expected to perform very similarly to ZSM in producing 74.7 mg/g of MAH+PAH at 600 °C.

Precisely Constructing Orbital-Coupled Fe─Co Dual-atom Sites for High-Energy-Efficiency Zn-Air/Iodide Hybrid Batteries.

Rechargeable Zn-air batteries (ZABs) are promising for energy storage and conversion. However, the high charging voltage and low energy efficiency hinder their commercialization. Herein, these challenges are addressed by employing precisely constructed multifunctional Fe-Co diatomic site catalysts (FeCo-DACs) and integrating iodide/iodate redox into ZABs to create Zinc-air/iodide hybrid batteries (ZAIHBs) with highly efficient multifunctional catalyst. The strong coupling between the 3d orbitals of Fe and Co weakens the excessively strong binding strength between active sites and intermediates, enhancing the catalytic activities for oxygen reduction/evolution reaction and iodide/iodate redox. Consequently, FeCo-DACs exhibit outstanding bifunctional oxygen catalytic activity with a small potential gap (ΔE=0.66V) and outstanding stability. Moreover, an outstanding catalytic performance toward iodide/iodate redox is obtained. Therefore, FeCo-DAC-based ZAIHBs exhibit high energy efficiency of up to 75% at 10mAcm-2 and excellent cycling stability (72% after 500h). This research offers critical insights into the rational design of DACs and paves the way for high-energy efficiency energy storage devices.

Design for all-round PHE/HER/OER sandwich nanostructure catalyst: Ultrathin nanosheet ZnIn2S4-encapsulated rich-Mo edge active site Mo2C-N Schottky junction

The development of efficient multifunctional catalyst remains a huge challenge due to their unsatisfactory oxygen/hydrogen intermediate species adsorption, ineffective kinetics rate, lack of active reaction sites. Herein, rich-Mo edge active sites in the molybdenum carbide (Mo2C) were created through nitrogen doping, which was used as cocatalyst to enhance the hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and photocatalytic hydrogen evolution (PHE) of ZnIn2S4 (ZIS). Mo2C-N/ZIS affords a remarkable HER activity with a low overpotential of 74 mV as well as excellent OER activity with a reduced overpotential of 250 mV at 10 mA·cm−2. The formed Schottky junction between Mo2C-N/ZIS are responsible for the enhanced PHE/HER/OER activity, which owns double transfer route beneficial to enhancing separation of photogenerated carriers and reducing bulk/surface recombination of ZIS. Specially, the density functional theory (DFT) calculations demonstrate that Mo2C-N/ZIS Schottky junction with optimal absorption energy for the hydrogen and oxygen intermediates.

Development of Multifunctional Catalysts for the Direct Hydrogenation of Carbon Dioxide to Higher Alcohols.

The direct hydrogenation of greenhouse gas CO2 to higher alcohols (C2+OH) provides a new route for the production of high-value chemicals. Due to the difficulty of C-C coupling, the formation of higher alcohols is more difficult compared to that of other compounds. In this review, we summarize recent advances in the development of multifunctional catalysts, including noble metal catalysts, Co-based catalysts, Cu-based catalysts, Fe-based catalysts, and tandem catalysts for the direct hydrogenation of CO2 to higher alcohols. Possible reaction mechanisms are discussed based on the structure-activity relationship of the catalysts. The reaction-coupling strategy holds great potential to regulate the reaction network. The effects of the reaction conditions on CO2 hydrogenation are also analyzed. Finally, we discuss the challenges and potential opportunities for the further development of direct CO2 hydrogenation to higher alcohols.

Controlled synthesis of M doped NiMoO4 (M = Co, Cu and Fe) for urea, freshwater and seawater oxidation reaction

Electrocatalytic splitting of urea or seawater for hydrogen production has become one of the most promising methods. In this paper, different foreign ions M (M = Co, Cu and Fe) are introduced into this NiMoO4 material by hydrothermal and impregnation methods. Their electrocatalytic properties were investigated in different electrolytes, such as urea, pure water and seawater. What is noteworthy is that the Co-NiMoO4/NF electrode exhibited superior urea oxidation properties (1.32 V @ 10 mA cm−2). The different reaction mechanisms result in the superior water oxidation performance of this Fe3+-NiMoO4/NF material. What is noteworthy is that the durability of the material needs to be improved. The promoted performance is attributed to rapid electron transfer and improved electrical conductivity. Density functional theory (DFT) also shows that this Fe-NiMoO4/NF electrode presents optimal water adsorption energy and improved electrical conductivity, thus improving the catalytic activity of the material because of introduction of Fe. The work provides novel views for the design of environmentally friendly and inexpensive multifunctional catalysts for urea, freshwater and seawater splitting reaction.

Transcending catalytic limits for methane decomposition: multi-functional basalt fiber-supported catalysts with membrane synergy

Transcending catalytic limits for methane decomposition: multi-functional basalt fiber-supported catalysts with membrane synergy

Periodic Adjacent Pd‐Fe Pair Sites for Enhanced Nitrate Electroreduction to Ammonia via Accelerating Proton Relay

AbstractRecently, bimetallic nanoparticles (NPs) are promising for driving nitrate (NO3 −) reduction reaction (NO3RR) to produce ammonia (NH3) due to their multiple active sites and electron redistribution via strong metal–metal interaction. However, the quantitatively determining the atomic configuration of the active sites and revealing their respective roles in NO3RR process are still challenged. Herein, the configuration of atomically ordered PdFe3 L12 intermetallic NPs into mesoporous carbon nanofibers (O‐PdFe3‐mCNFs) is reported as an efficient NO3RR catalyst for NH3 synthesis. Compared to the face‐centered cubic one, the O‐PdFe3‐mCNFs demonstrate a high NO3− removal of 98.3% within 270 min with a large NH3 yield rate of 1014.2 µmol h−1 cm−2. The detailed in situ and theoretical analysis reveals that the high performance of O‐PdFe3‐mCNFs is attributed to the synergetic effect from the periodic adjacent Pd‐Fe pair sites at the ordered (110) facet via accelerating proton relay, where the Fe sites show preferable stabilization of nitrogen−oxygen (*NO) intermediates while Pd sites serve as proton reservoir for *NO hydrogenation. Moreover, the strong d‐d orbital hybridization tunes d‐band center of the alloy NPs and effectively modulates the adsorption energy of *NO3− and *NO. This synergetic electrocatalyst design offers a new avenue for developing highly efficient multifunctional NO3RR catalysts.

Design of Multifunctional Electrocatalysts for ORR/OER/HER/HOR: Janus Makes Difference.

Multifunctional electrocatalysts for hydrogen evolution reaction (HER), hydrogen oxidation reaction (HOR), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) have broad application prospects; However, realization of such kinds of materials remain difficulties because it requires the materials to have not only unique electronic properties, but multiple active centers to deal with different reactions. Here, employing density functional theory (DFT) computations, it is demonstrated that by decorating the Janus-type 2D transition metal dichalcogenide (TMD) of TaSSe with the single atoms, the materials can achieve multifunctionality to catalyze the ORR/OER/HER/HOR. Out of sixteen catalytic systems, Pt-VS (i.e., Pt atom embedded in the sulfur vacancy), Pd-VSe, and Pt-VSe@TaSSe are promising multifunctional catalysts with superior stability. Among them, the Pt-VS@TaSSe catalyst exhibits the highest activity with theoretical overpotentials ηORR = 0.40V, ηOER = 0.39V, and ηHER/HOR = 0.07V, respectively, better than the traditional Pt (111), IrO2 (110). The interplays between the catalyst and the reaction intermediate over the course of the reaction are then systematically investigated. Generally, this study presents a viable approach for the design and development of advanced multifunctional electrocatalysts. It enriches the application of Janus, a new 2D material, in electrochemical energy storage and conversion technology.