Strong Electronic Interaction Research Articles

In situ construction of layered transition metal phosphides/sulfides heterostructures for efficient hydrogen evolution in acidic and alkaline media

Construction of electrocatalysts with exceptional intrinsic activity and rich active sites has proved to be an effective strategy for remarkably enhancing the activity of the hydrogen evolution reaction (HER). In this work, durable and highly efficient layered Re2P/ReS2 (RePS) heterostructures were successfully fabricated by an in-situ phosphating layered ReS2. Taking advantage of the unique layered structure can provide abundant reaction active sites and the strong electronic interaction between ReS2 and Re2P can enhance the intrinsic activity, the optimized RePS electrocatalysts show superior catalytic activities of 69 and 57 mV at 10 mA cm−2 for HER in alkaline and acidic media, respectively. The density functional theory results suggest that the formed heterostructures between ReS2 and Re2P play an important role in optimizing the catalytic kinetics of the electrocatalysts. This work not only demonstrates that modulation of the electronic structure of catalysts is an efficient way to improve the HER activity but also confirms that the layered RePS heterostructure is a promising candidate for robust and high performance HER catalysts.

Strong Interactions between Au Nanoparticles and BiVO4 Photoanode Boosts Hole Extraction for Photoelectrochemical Water Splitting.

Strong metal-support interaction (SMSI) is widely proposed as a key factor in tuning catalytic performances. Herein, the classical SMSI between Au nanoparticles (NPs) and BiVO4 (BVO) supports (Au/BVO-SMSI) is discovered and used innovatively for photoelectrochemical (PEC) water splitting. Owing to the SMSI, the electrons transfer from V4+ to Au NPs, leading to the formation of electron-rich Au species (Auδ-) and strong electronic interaction (i.e., Auδ--Ov-V4+), which readily contributes to extract photogenerated holes and promote charge separation. Benefitted from the SMSI effect, the as-prepared Au/BVO-SMSI photoanode exhibits a superior photocurrent density of 6.25 mA cm-2 at 1.23 V versus the reversible hydrogen electrode after the deposition of FeOOH/NiOOH cocatalysts. This work provides a pioneering view for extending SMSI effect to bimetal oxide supports for PEC water splitting, and guides the interfacial electronic and geometric structure modulation of photoanodes consisting of metal NPs and reducible oxides for improved solar energy conversion efficiency.

Strong Interactions between Au Nanoparticles and BiVO4 Photoanode Boosts Hole Extraction for Photoelectrochemical Water Splitting

AbstractStrong metal‐support interaction (SMSI) is widely proposed as a key factor in tuning catalytic performances. Herein, the classical SMSI between Au nanoparticles (NPs) and BiVO4 (BVO) supports (Au/BVO‐SMSI) is discovered and used innovatively for photoelectrochemical (PEC) water splitting. Owing to the SMSI, the electrons transfer from V4+ to Au NPs, leading to the formation of electron‐rich Au species (Auδ−) and strong electronic interaction (i.e., Auδ−‐Ov‐V4+), which readily contributes to extract photogenerated holes and promote charge separation. Benefitted from the SMSI effect, the as‐prepared Au/BVO‐SMSI photoanode exhibits a superior photocurrent density of 6.25 mA cm−2 at 1.23 V versus the reversible hydrogen electrode after the deposition of FeOOH/NiOOH cocatalysts. This work provides a pioneering view for extending SMSI effect to bimetal oxide supports for PEC water splitting, and guides the interfacial electronic and geometric structure modulation of photoanodes consisting of metal NPs and reducible oxides for improved solar energy conversion efficiency.

In situ growth of highly wrinkled 3D volcano-like Fe3S4/Ni3S2/WO3/NiFe LDH/NF electrocatalyst for overall water splitting

The rational design of efficient, cost-effective, and durable electrocatalysts is crucial for the realization of hydrogen production through water splitting. The present study describes the synthesis of a novel three-dimensional (3D) volcano-like Fe3S4/Ni3S2/WO3/NiFe LDH/NF (Layered Double Hydroxides/Nickel Foam) electrocatalyst with a highly wrinkled structure through a two-step hydrothermal method. The as-synthesized electrocatalyst exhibits an exceptionally low overpotential of 77 mV for the hydrogen evolution reaction (HER) and 131 mV for the oxygen evolution reaction (OER) at a current density of 10 mA cm−2, owing to the unique morphology and strong electronic interactions between Fe3S4, Ni3S2 and WO3 heterostructures. The Fe3S4/Ni3S2/WO3/NiFe LDH/NF electrocatalyst demonstrates exceptional performance in overall water splitting when employed as both anode and cathode, achieving a current density of 10 mA cm−2 at an impressively low cell voltage of 1.5 V as well as exhibiting remarkable durability with little degradation over a period of 12 hours. This study presents a straightforward approach for the synthesis of highly efficient and durable non-noble metal catalysts for overall water splitting under hydrothermal conditions.

Dynamic Reconfiguration and Local Polarization of NiFe-Layered Double Hydroxide-Bi2MoO6- x Heterojunction for Enhancing Piezo-Photocatalytic Nitrogen Oxidation to Nitric Acid.

Constructing heterojunctions with vacancies has garnered substantial attention in the field of piezo-photocatalysis. However, the presence of interfacial vacancies can serve as charge-trapping sites, leading to the localization of electrons and hindering interfacial charge transfer. Herein, dual oxygen vacancies in the NiFe-layered double hydroxide and Bi2MoO6- x induced interfacial bonds have been designed for the piezo-photocatalytic N2 oxidation to NO3 -. Fortunately, it achieves sensational nitric acid production rates (7.23mg g-1 h-1) in the absence of cocatalysts and sacrificial agents, which is 6.03 times of pure Bi2MoO6 that under ultrasound and light illumination. Theoretical and experimental results indicate that interfacial bonds act as "charge bridge" and "strain center" to break the carrier local effect and negative effects with piezocatalysis and photocatalysis for promoting exciton dissociation and charge transfer. Moreover, the strong electronic interaction of the interfacial bond induces internal reconstruction under ultrasound for promoting the local polarization and adsorption of N2, which accelerates the fracture of the N≡N bonds and reduces the activation energy of the reaction. The research not only establishes a novel approach for optimizing the combined effects of piezo-catalysis and photocatalysis, but also achieves equilibrium between the synergistic impacts of vacancies and heterojunctions.

Optimizing the adsorption of intermediates through modulating Mn d-band centers by the Mn-Ce heterojunction for high-performance lithium-oxygen batteries

Admitting that rare-earth (RE)-based transition metal oxides (TMO) are emerging as a promising catalyst for lithium-oxygen (Li-O2) batteries, the understanding of their electrocatalytic mechanism and active sites remains ambiguous. In this study, CeO2 nanoparticles modified MnOOH nanowires (CeO2@MnOOH NWs) is prepared by a simple solvothermal method as highly effective cathode catalysts for Li-O2 batteries. The incorporation of CeO2 nanoparticles into MnOOH facilitates a robust interaction between the 3d electronic state of MnOOH and the 4f electronic state of CeO2 at the Fermi level (Ef). The strong electron interaction at the heterogeneous interface between MnOOH and CeO2 promotes internal electron transfer. Compared to pristine MnOOH, the prepared CeO2@MnOOH NWs exhibits enhanced electrocatalytic activity and improved electrocatalytic stability. According to experimental analysis and density functional theory (DFT) results, it is demonstrated that there is a slight negative shift in the d-band center of the Mn site, resulting in faster electron transfer rates and higher conductivity. This acceleration of charge transfer optimizes the adsorption strength of the oxygen-containing intermediate (LiO2), thereby promoting the kinetics of the oxygen reduction/evolution reactions (ORR/OER) and reducting the reaction over-potential. As a result, the electrochemical performances of Li-O2 batteries are greatly enhanced.

Ultrafine Ni-MoOx Nanoparticles Anchored on Nitrogen-Doped Carbon Nanosheets: A Highly Efficient Noble-Metal-Free Catalyst for Ammonia Borane Hydrolysis.

The development of low-cost and high-efficiency catalysts for the hydrolytic dehydrogenation of ammonia borane (AB, NH3BH3) is still a challenging technology. Herein, ultrafine MoOx-doped Ni nanoparticles (~3.0 nm) were anchored on g-C3N4@glucose-derived nitrogen-doped carbon nanosheets via a phosphate-mediated method. The strong adsorption of phosphate-mediated nitrogen-doped carbon nanosheets (PNCS) for metal ions is a key factor for the preparation of ultrasmall Ni nanoparticles (NPs). Notably, the alkaline environment formed by the reduction of metal ions removes the phosphate from the PNCS surface to generate P-free (P)NCS so that the phosphate does not participate in the subsequent catalytic reaction. The synthesized Ni-MoOx/(P)NCS catalysts exhibited outstanding catalytic properties for the hydrolysis of AB, with a high turnover frequency (TOF) value of up to 85.7 min-1, comparable to the most efficient noble-metal-free catalysts and commercial Pt/C catalyst ever reported for catalytic hydrogen production from AB hydrolysis. The superior performance of Ni-MoOx/(P)NCS can be ascribed to its well-dispersed ultrafine metal NPs, abundant surface basic sites, and electron-rich nickel species induced by strong electronic interactions between Ni-MoOx and (P)NCS. The strategy of combining multiple modification measures adopted in this study provides new insights into the development of economical and high-efficiency noble-metal-free catalysts for energy catalysis applications.

Solvent-free selective hydrogenation of nitroaromatics to azoxy compounds over Co single atoms decorated on Nb2O5 nanomeshes

The solvent-free selective hydrogenation of nitroaromatics to azoxy compounds is highly important, yet challenging. Herein, we report an efficient strategy to construct individually dispersed Co atoms decorated on niobium pentaoxide nanomeshes with unique geometric and electronic properties. The use of this supported Co single atom catalysts in the selective hydrogenation of nitrobenzene to azoxybenzene results in high catalytic activity and selectivity, with 99% selectivity and 99% conversion within 0.5 h. Remarkably, it delivers an exceptionally high turnover frequency of 40377 h–1, which is amongst similar state-of-the-art catalysts. In addition, it demonstrates remarkable recyclability, reaction scalability, and wide substrate scope. Density functional theory calculations reveal that the catalytic activity and selectivity are significantly promoted by the unique electronic properties and strong electronic metal-support interaction in Co1/Nb2O5. The absence of precious metals, toxic solvents, and reagents makes this catalyst more appealing for synthesizing azoxy compounds from nitroaromatics. Our findings suggest the great potential of this strategy to access single atom catalysts with boosted activity and selectivity, thus offering blueprints for the design of nanomaterials for organocatalysis.

Highly-dispersed 2D NiFeP/CoP heterojunction trifunctional catalyst for efficient electrolysis of water and urea

The electrocatalytic production of “green hydrogen”, such as through the electrolysis of water or urea has been vigorously advocated to alleviate the energy crisis. However, their electrode reactions including oxygen evolution reaction (OER), urea oxidation reaction (UOR), and hydrogen evolution reaction (HER) all suffer from sluggish kinetics, which urgently need catalysts to accelerate the processes. Herein, we design and prepare an OER/UOR/HER trifunctional catalyst by transforming the homemade CoO nanorod into a two-dimensional (2D) ultrathin heterojunction nickel–iron-cobalt hybrid phosphides nanosheet (NiFeP/CoP) via a hydrothermal-phosphorization method. Consequently, a strong electronic interaction was found among the Ni2P/FeP4/CoP heterogeneous interfaces, which regulates the electronic structure. Besides the high mass transfer property of 2D nanosheet, Ni2P/FeP4/CoP displays improved OER/UOR/HER performance. At 10 mA cm−2, the OER overpotential reaches 274 mV in 1.0 M KOH, and the potential of UOR is only 1.389 V in 1.0 M KOH and 0.33 M urea. More strikingly, the two-electrode systems for electrolysis water and urea-assisted electrolysis water assembled by NiFeP/CoP could maintain long-term stability for 35 h and 12 h, respectively. This work may help to pave the way for upcoming research horizons of multifunctional electrocatalysts.

Robust pseudocapacitive Na+ intercalation induced by MoS2 on active Mo2C current collector interface for high areal capacity sodium-ion batteries

Sodium-ion batteries (SIBs) have emerged as compelling alternatives in the realm of electrochemical energy devices, poised to substitute lithium-ion batteries (LIBs). The primary challenge encompasses not only the scarcity of anode materials exhibiting exceptional Na+ storage capacity but also the endeavor to achieve high areal capacity. To address this challenge, a comprehensive strategy is proposed that entails utilizing a highly conductive molybdenum dicarbide (Mo2C) current collector (denoted as CCM) as a supporting scaffold for the bottom-up growth of molybdenum disulfide nanosheets (MoS2, serving as the main active component) (denoted as CCM@MoS2). The CCM improves interfacial bonding with MoS2 nanosheets and offers additional capacity to accommodate the increased Na+ insertion activity. Both theoretical and kinetic analyses reveal that the enhanced Na+ storage properties primarily stem from favorable adsorption energy, reduced diffusion barrier, and intercalation pseudocapacitance due to the strong electronic interfacial interaction between active CCM and MoS2. Hence, the as-prepared optimized CCM@MoS2 electrode exhibits a superior areal capacity of 6.36 mAh cm−2 at 0.4 mA cm−2, excellent rate capability of 1.02 mAh cm−2 at 24 mA cm−2 and long cycle life up to 500 cycles at 4 mA cm−2. Interesting, our as-prepared CCM@MoS2 electrode shows better performance for Na+ storage than Li+ storage at higher current density, affirming the enhanced kinetics in our architecture. This work proposes a rational strategy to enhance the areal capacity and stability of MoS2-based anode for SIBs and beyond.

Structural, hydrogen storage capacity, electronic and optical properties of Li-N-H hydrogen storage materials from first-principles investigation

Although Li-N-H systems are promising hydrogen storage materials, the structural feature, phonon dynamical, electronic and optical properties of Li-N-H systems are unclear. To solve these problems, we apply the first-principles method to study the structural stability, hydrogen storage capacity, dehydrogenation energy, electronic and optical properties of three Li-N-H systems (Li4NH, Li2NH and LiNH2). The calculated results show that Li4NH and LiNH2 are thermodynamic and dynamical stabilities. Although Li2NH is a dynamical instability, it is a thermodynamic stability at the ground state. Importantly, the calculated gravimetric hydrogen storage capacity is 1.19 wt% for Li4NH, 3.35 wt% for Li2NH and 8.02 wt% for LiNH2, respectively. Essentially, the high hydrogen storage capacity of LiNH2 is related to the formation of [NH2] group due to the strong electronic interaction between N and H. Furthermore, Li2NH shows metallic behavior. However, the calculated band gap is 1.958 eV for Li4NH and 3.016 eV for LiNH2. The change of band gap of Li-N-H hydrides is demonstrated by the dielectric functional. In addition, this LiNH2 with high concentration of hydrogen has better storage optical properties compared to Li4NH and Li2NH.

Enhanced stability and catalytic activity of subnanometric platinum cluster by surface doping of zirconium in CeO2

There has been a continuous effort to improve the thermal stability of subnanometric platinum (Pt) cluster (<2 nm) catalyst because Pt cluster on CeO2 support can be mobile and aggregated into nanoparticle on heating at elevated temperatures, yet this great challenge remains. In this study, a strategy is reported to improve the thermal stability of subnanometric Pt cluster by hydrothermal deposition method. Based on this method, zirconium (Zr) was precisely doped on surface of Ce0.95Zr0.05O2 by accurate control of Pt subnanometric cluster size. The surface doping of Zr is favorable for forming the Zr–O–Ce site and activating surface lattice oxygen atoms, which results in strong electronic interactions to stabilize the Pt subnanometric cluster. After high-temperature aging treatment at 1000 °C/4 h, the single atom Pt supported on CeO2 is aggregated into larger sized (>3 nm) nanoparticle. In contrast, the single atom Pt supported on Ce0.95Zr0.05O2 displays less agglomeration into subnanometric cluster with size of (1.4 ± 0.3) nm. Moreover, the CO oxide catalytic performance of Ce0.95Zr0.05O2–Pt is 26 % and 31 % higher than that of CeO2–Pt and commercial Al2O3–Pt catalysts, respectively. The experimental and density functional theory (DFT) calculations indicate that the Zr–O–Ce site and Pt subnanometric cluster interface have more defect sites and active oxygen species than CeO2–Pt interface, which activate the Mars van Krevelen (MvK) mechanism, facilitating the catalytic performance.

ZIF-67-derived petal-like Co(OH)2-MoO3/NF layered nanosheets as a promising electrocatalyst for oxygen evolution reaction

The development of high-performance and cost-effective electrocatalysts for oxygen evolution reactions (OER) is key to renewable energy conversion and storage technologies. In this paper, a hierarchical Co(OH)2-MoO3 nanosheets with petal-like architecture was prepared by a simple one-step hydrothermal method using ZIF-67/NF as a precursor, and it was used as a direct electrocatalyst for OER. Notably, this petal-like Co(OH)2-MoO3/NF layered nanosheets not only prevent the agglomeration of nanostructured material, but also facilitate the complete penetration and diffusion of electrolyte.In addition, due to the strong electronic interaction between Co(OH)2 and MoO3 in the Co(OH)2-MoO3/NF system, Co(OH)2-MoO3/NF exhibits excellent electrocatalytic OER performance. It has a low overpotential of 273 mV at 10 mA cm−2 and excellent stability.This study provides a simple and effective strategy for the rational design and structural evolution of MOF-derived materials to achieve inexpensive and effective electrocatalysis.

Ag engineered NiFe-LDH/NiFe2O4 Mott-Schottky heterojunction electrocatalyst for highly efficient oxygen evolution and urea oxidation reactions

Efficient and durable electrocatalysts with sufficient active sites and high intrinsic activity are essential for advancing energy-saving hydrogen production technology. In this study, a Mott-Schottky heterojunction electrocatalyst with Ag nanoparticles in-situ grown on NiFe layered double hydroxides (NiFe-LDH)/NiFe2O4 nanosheets (Ag@NiFe-LDH/NiFe2O4) were designed and successfully synthesized through a hydrothermal process and subsequent spontaneous redox reaction. The in-situ growth of metallic Ag on semiconducting NiFe-LDH/NiFe2O4 triggers a strong electron interaction across the Mott-Schottky interface, leading to a significant increase in both the intrinsic catalytic activity and the electrochemical active surface area of the heterojunction electrocatalyst. As a result, the Ag@NiFe-LDH/NiFe2O4 demonstrates impressive oxygen evolution reaction (OER) performance in alkaline KOH solution, achieving a low overpotential of 249 mV at 100 mA cm−2 and a Tafel slope of 42.79 mV dec−1. When the self-supported Ag@NiFe-LDH/NiFe2O4 is coupled with the Pt/C electrocatalyst, the alkaline electrolyzer reaches a current density of 10 mA cm−2 at a cell voltage of only 1.460 V. Furthermore, X-ray photoelectron spectroscopy and in-situ Raman analysis reveal that the Ni(Fe)OOH is the possible active phase for OER in the catalyst. In addition, when employed for UOR catalysis, the Ag@NiFe-LDH/NiFe2O4 also displays intriguing activity with an ultralow potential of 1.389 V at 50 mA cm−2. This work may shed light on the rational design of multiple-phase heterogeneous electrocatalysts and demonstrate the significance of interface engineering in enhancing catalytic performance.

Structure solution and refinement of beam-sensitive nano-crystals

Radiation sensitive materials are among the most difficult materials to study, even more so if they exist only as nanometer-sized particles, where their size is either intentional because of enhanced properties at the nano-scale or it is unintentional because it is impossible to obtain bigger particles of the same structure. In both cases characterization methods need to be optimized to get the most information out of these particles before the radiation damages them to a point where their structure is altered. When the particles are crystallized, both characteristics, the small size and the beam sensitivity, call for electron diffraction as a privileged investigation tool. The strong interaction of electrons (as compared to X-rays) with matter allows single crystal diffraction experiments on nanometer-sized crystals and for the same amount of beam damage, electron diffraction yields more information than X-rays. These inherent advantages of electron diffraction are optimized in the recently developed low-dose electron diffraction tomography (LD-EDT) by minimizing the necessary dose for a complete data collection. In this contribution we show that in some cases even doses as low as 2 e-/Ų can induce damage in crystal structures that inhibit a correct structure refinement. However, by LD-EDT we can obtain data using extremely low doses that don’t alter the structure which make it then possible not only to solve crystal structures but also to refine them using dynamical diffraction theory. Here a synthetic oxide containing volatile Na and a metal-organic framework are given as examples. A dynamical refinement of the structures is possible with data sets requiring a dose of less than 0.15 e-/Ų.

Electron-interactive 1D porous vertical NiCo2O4 nanowire and 3D N-doped graphene aerogel enable high hydroxyl-ion adsorption capacity for superior energy storage

Supercapacitors are a kind of highly efficient energy-storage device with long cycle life and high power density, however, their specific capacitance is insufficient for further application and development. In this work, a novel composite with one-dimensional (1D) NiCo2O4 nanowire arrays (NiCo2O4-NWA) vertically supported on three-dimensional (3D) nitrogen-doped graphene aerogel (NGA) is designed and facilely realized by hydrothermal reaction and thermal treatment. The NiCo2O4 nanowires, with length of ∼1 μm and diameter of ∼25 nm, display a porous structure and are regularly arranged on both sides of the sheets in nitrogen-doped graphene aerogel. The aerogel-supporting NiCo2O4 nanowires demonstrate a remarkably high specific capacitance of 2742 F g−1 at 1 A g−1, and an outstanding cyclic stability with capacitance retention of 90% even after 10,000 cycles at 80 A g−1. The density functional theory calculation shows the narrow band gap (0.32 eV) and strong electronic interaction and hydroxyl-ion adsorption effect of NiCo2O4 supported on NGA, resulting in superior specific capacitance and energy storage performance. The 3D nitrogen-doped graphene aerogel supporting 1D nanowire arrays represent a promising high-performance electrode material for application in the supercapacitors and other electrochemical energy-conversion and storage equipment.

Porous rod-like structured ternary nitride heterocatalyst Co3Mo3N/Ni3Mo3N for efficient and stable hydrogen evolution reaction

Heterostructure electrocatalysts have garnered widespread attention for effectively enhancing electrocatalytic activity. However, less attention has been paid to ternary nitride heterostructure catalysts for the hydrogen evolution reaction (HER), and their synthesis remains challenging. In this study, a Co3Mo3N/Ni3Mo3N heterostructure catalyst on nickel foam (NF) is designed and prepared via high-temperature nitridation of the heterostructured precursor. The resulting 1D/3D hierarchical structure electrode, featuring rich heterointerfaces, provides abundant active sites, enhancing mass transport and charge transfer. Experimental results reveal strong electronic interactions at the heterointerface, while density functional theory (DFT) calculations establish that Co3Mo3N/Ni3Mo3N possesses a lower water dissociation energy barrier and optimized hydrogen adsorption energy. Consequently, it demonstrates excellent HER performance, exhibiting low overpotentials of 36 mV in alkaline and 58 mV in neutral media at 10 mA cm−2. This study presents an innovative approach to designing ternary nitride heterostructure catalysts with enhanced HER activity, applicable to other heterostructure catalysts.

Local coordination and electronic interactions of Pd/MXene via dual‐atom codoping with superior durability for efficient electrocatalytic ethanol oxidation

AbstractCatalyst design relies heavily on electronic metal‐support interactions, but the metal‐support interface with an uncontrollable electronic or coordination environment makes it challenging. Herein, we outline a promising approach for the rational design of catalysts involving heteroatoms as anchors for Pd nanoparticles for ethanol oxidation reaction (EOR) catalysis. The doped B and N atoms from dimethylamine borane (DB) occupy the position of the Ti3C2 lattice to anchor the supported Pd nanoparticles. The electrons transfer from the support to B atoms, and then to the metal Pd to form a stable electronic center. A strong electronic interaction can be produced and the d‐band center can be shifted down, driving Pd into the dominant metallic state and making Pd nanoparticles deposit uniformly on the support. As‐obtained Pd/DB–Ti3C2 exhibits superior durability to its counterpart (∼14.6% retention) with 91.1% retention after 2000 cycles, placing it among the top single metal anodic catalysts. Further, in situ Raman and density functional theory computations confirm that Pd/DB–Ti3C2 is capable of dehydrogenating ethanol at low reaction energies.

Pd nanoflakes epitaxially grown on defect MoS2 nanosheets for enhanced nitroarenes hydrogenation to anilines

Hydrogenation of nitroarenes to anilines under mild conditions is attractive from both theoretical and practical viewpoints. Here, high-performance catalyst with layered Pd nanoparticles epitaxially growing on ultrathin MoS2 nanosheets (Pd/MoS2) were prepared. It shows surprisingly high catalytic activity, selectivity and stability for hydrogenation of various nitroarenes to corresponding anilines; the turnover frequency is one or two magnitudes higher than conventional Pd-based catalysts. Surface sulfur vacancies are formed on MoS2 nanosheets with low formation energy barrier. These S vacancies provide efficient positions for adsorbing Pd atoms, which enables facile cleavage of N–O bond as result of strong interfacial electron interaction that decreases activation energy by 0.41 eV in comparison with conventional Pd catalysts. In situ spectroscopy and DFT calculation results reveal a dual-site mechanism, in which surface Pd sites adsorb and dissociate H2 into active H*, and then readily reacts with nearby activated nitroarene to form aniline on interfacial Pd-MoS2 sites.

Strong electronic metal-support interactions as a strategy for boosting selective hydrogenation of resorcinol to 1,3-cyclohexanedione

Strong electronic metal-support interactions (EMSIs) present in supported metal catalysts play a crucial role in determining their catalytic performances. In this study, we demonstrate the successful utilization of nanosized TiO2 (∼8 nm) as a carrier to achieve highly dispersed Pd clusters (∼0.59 nm) with robust EMSIs, even at a high Pd loading of 5 wt%. The presence of surface defects in nanosized TiO2 facilitates the anchoring of Pd clusters onto the support surface, leading to enhanced EMSIs between TiO2 and Pd. The prepared Pd/TiO2 catalyst delivers drastically improved catalytic property in the hydrogenation of resorcinol (RES), achieving >99 % conversion and >99 % selectivity towards 1,3-cyclohexanedione (1,3-CHD) within 60 min at 2 MPa hydrogenation pressure and 373 K. This performance is superior to that of Pd nanoparticles on TiO2 support with a larger particle size of ∼200 nm, which only achieves 80 % conversion and 37 % selectivity to 1,3-CHD. Both experimental data and theoretical calculations confirm that TiO2 donates electrons to the Pd clusters, thereby enhancing the hydrogenation properties of RES. Specifically, the electron-deficient TiO2 favors the adsorption and activation of phenoxy anion, while the electron-enriched Pd induces a nonplanar conformation of the adsorbed RES molecules and facilitates the electrophilic attack of adsorbed hydrogen on RES by weakening the strength of hydrogen adsorption. Furthermore, the Pd/TiO2 catalyst exhibits excellent recyclability, maintaining its efficiency over 7 cycles, attributed to the stabilizing effect of nanosized TiO2 on Pd clusters. The simple design strategy presented in this work enables the development of supported metal catalysts with significant EMSIs and is expected to attract more attention in future research.