Stability Of Active Sites Research Articles

Platinum Nanoparticles Bonded with Carbon Nanotubes for High-Performance Ampere-Level All-Water Splitting.

Platinum nanoparticles loaded on a nitrogen-doped carbon nanotubes exhibit a brilliant hydrogen evolution reaction (HER) in an alkaline solution, but their bifunctional hydrogen and oxygen evolution reaction (OER) has not been reported due to the lack of a strong Pt-C bond. In this work, platinum nanoparticles bonded in carbon nanotubes (Pt-NPs-bonded@CNT) with strong Pt-C bonds are designed toward ultralow overpotential water splitting ability in alkaline solution. Benefit from the strong interaction between platinum and high conductivity carbon nanotube substrates through the Pt-C bond also the platinum nanoparticles bonded in carbon nanotube can provide more stable active sites, as a result, the Pt-NPs-bonded@CNT exhibits excellent hydrogen evolution in acid and alkaline solution with ultralow overpotential of 0.19 and 0.23 V to reach 1000 mA cm-2, respectively. Besides, it shows superior oxygen evolution electrocatalysis in alkaline solution with a low overpotential of 1.69 V at 1000 mA cm-2. Furthermore, it also exhibits high stability over 110 h against the evolution of oxygen and hydrogen at 1000 mA cm-2. This strategy paves the way to the high performance of bifunctional electrocatalytic reaction with extraordinary stability originating from optimized electron density of metal active sites due to strong metal-substrate interaction.

Catalytic Hydrogenation of γ-Butyrolactone to Butanediol over a High-Performance Cu-SiO2 Catalyst

High-performance Cu catalysts were developed for the selective hydrogenation of γ-butyrolactone (GBL) to 1,4-butanediol (BDO). Among the various catalysts prepared by ammonia evaporation (AE) and impregnation (IM) methods with silica or MFI zeolite supports, the 5% Cu-SiO2-AE catalyst was the best one. It exhibited 95% selectivity for BDO and 71% conversion of GBL after 2–8 h reaction at 200 °C and 4 MPa H2, with high stability in five-cycle runs. Comprehensive characterizations showed that the AE method favored generating nano Cu particles with an average size of 2.9 nm on the 5% Cu-SiO2-AE catalyst. The silica support derived from a sol demonstrated an advantage over the MFI zeolite in the preparation of a highly dispersed and stable Cu catalyst, in view of its anti-sintering and robust composition of Cu0, Cu+, and Cu2+ in the cycling operation. The reaction pathways for GBL to BDO over the Cu catalysts were found to commonly involve reversible reactions of hydrogenation and dehydrogenation, along with subsequent dehydration to form THF. The high performance of the Cu catalysts in the conversion of GBL to BDO was attributed to the high dispersion of Cu, the presence of stable active sites, and fewer strong acid sites in the catalyst.

Engineering stable active Cu0-Cuσ+ sites via in situ surface reconstruction over Cu/CeO2 catalyst for the hydrogenation of carbon-oxygen bonds

Cu/CeO2 catalysts have been wildly used for the hydrogenation of carbon-oxygen bonds reactions due to their excellent catalytic performance. It is widely accepted that the Cu0-Cuσ+ interface could be the primary active sites during the reaction, but how to form and maintain highly dispersed such species remains challenging under the reaction conditions of high temperature and H2 partial pressure. In this work, we proposed an effective strategy to construct stable Cu0-Cuσ+ interface sites over the Cu/CeO2 catalysts by in situ N2O-involved oxidation treatment. It was evidenced that the sequential oxidation-reduction by N2O and H2 broke the grain boundaries of Cu nanoparticles and therefore facilitated the formation of the active Cu0-Cuσ+ sites, leading to an enhanced activity. However, a rapid deactivation was observed after this temporary enhancement due to the aggregation of copper species. We further introduced some additional cerium species during catalyst preparation. The 16Cu/CeO2-1Ce catalyst prepared by post-impregnation of 1 wt% cerium achieved a stable performance of 90.6% MA conversion after the N2O-involved oxidation treatment, which was much higher than that of 26.2% over the 16Cu/CeO2 catalyst. It was demonstrated that the strong interaction between the formed CeO2 and reconstructed Cu species prevented the metal sintering and increased the fraction of the Cu0-Cuσ+ sites. This method that combined in situ N2O-involved oxidation treatment and cerium modification may offer potential in engineering stable active sites for high-performance catalysts in the hydrogenation of carbon-oxygen bonds.

Phase reconfiguration of heterogeneous CoFeS/CoNiS nanoparticles for superior battery-type supercapacitors

Developing advanced battery-type materials with abundant active sites, high conductivity, versatile morphologies, and hierarchically porous structures is crucial for realizing high-quality hybrid supercapacitors. Herein, heterogeneous FeS@NiS is synthesized by cationic Co doping via surface-structure engineering. The density functional theory (DFT) theoretical calculations are firstly performed to predict the advantages of Co dopant by improving the OH− adsorption properties and adjusting electronic structure, benefiting ions/electron transfer. The dynamic surface evolution is further explored which demonstrates that CoFeS@CoNiS could be quickly reconstructed to Ni(Co)Fe2O4 during the charging process, while the unstable structure of the amorphous Ni(Co)Fe2O4 results in partial conversion to Ni/Co/FeOOH at high potentials, which contributes to the more reactive active site and good structural stability. Thus, the free-standing electrode reveals excellent electrochemical performance with a superior capacity (335.6 mA h g−1, 2684 F g−1) at 3 A g−1. Furthermore, the as-fabricated device shows a quality energy density of 78.1 W h kg−1 at a power density of 750 W kg−1 and excellent cycle life of 92.1% capacitance retention after 5000 cycles. This work offers a facile strategy to construct versatile morphological structures using electrochemical activation and holds promising applications in energy-related fields.

Catalytic hydrogenation of CO2 to DME on surface Cu via highly efficient electron redistribution at the Cu0/Cu+ interface

The activity of copper-based bifunctional catalysts for CO2 hydrogenation to dimethyl ether (DME) is generally constrained by the loss of Cu0 sites during the reaction. Previous studies have focused on introducing additional elements to improve the stability of active sites. In this study, an electron redistribution of the Cu/Cu2O interface was constructed. Surface Cu0 provides active sites for H2 adsorption and dissociation, and the Cu0/Cu+ interface sites are more beneficial for the activation and hydrogenation of CO2. The Ointer–H moieties that form at interface sites reduce the reaction energy barrier of CH3OH synthesis, and the decomposition of H2COOH* to CH2O* species is the rate-limiting step. In addition, the Cu0/Cu+ interface restricts the migration of copper species and protects the weak acid sites of HZSM-5 during the reaction. The present work provides an atomic-level description of H2 dissociation and CO2 activation by Cu0/Cu+ surface and interface sites.

Single-atom platinum with asymmetric coordination environment on fully conjugated covalent organic framework for efficient electrocatalysis

Two-dimensional (2D) covalent organic frameworks (COFs) and their derivatives have been widely applied as electrocatalysts owing to their unique nanoscale pore configurations, stable periodic structures, abundant coordination sites and high surface area. This work aims to construct a non-thermodynamically stable Pt-N2 coordination active site by electrochemically modifying platinum (Pt) single atoms into a fully conjugated 2D COF as conductive agent-free and pyrolysis-free electrocatalyst for the hydrogen evolution reaction (HER). In addition to maximizing atomic utilization, single-atom catalysts with definite structures can be used to investigate catalytic mechanisms and structure-activity relationships. In this work, in-situ characterizations and theoretical calculations reveal that a nitrogen-rich graphene analogue COF not only exhibits a favorable metal-support effect for Pt, adjusting the binding energy between Pt sites to H* intermediates by forming unique Pt-N2 instead of the typical Pt-N4 coordination environment, but also enhances electron transport ability and structural stability, showing both conductivity and stability in acidic environments.

Co─Mn Bimetallic Nanowires by Interfacial Modulation with/without Vacancy Filling as Active and Durable Electrocatalysts for Water Splitting.

Active and stable nonnoble electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are required for water splitting by sustainable electricity. Here, Mn bonded with O and P is incorporated to modulate Co3S4 and Co2P respectively to enhance the catalytic activity and extend the catalyst lifetime. Mn3O4 adjusts the electronic structure of Co3S4 and Co atom fills the oxygen vacancy in Mn3O4. The interfacial interaction endows Co3S4/Mn3O4 to a lower reaction barrier due to ideal binding energies for OER intermediates. Structure stability of active sites and enhanced Co─S bonds by Operando Raman spectroscopy and theoretical calculations reduce the dissolution of Co3S4/Mn3O4, resulting in a lifetime of 500h at 50mAcm-2 for OER. The modulation of Co2P by MnP weakens the interaction between Co sites and adsorbed H*, achieving a high activity under a large current for HER. The assembled electrolyzer affords 50mAcm-2 at 1.58V and exhibits a lifetime of 350h at 50mAcm-2. The calculations disclose the electron interaction for the activity and stability, as well as the enhanced conductivity. The findings develop new avenues toward promoting catalytic activity and stability, making Co─Mn bimetallic nanowires efficient electrocatalysts for nonnoble water electrolyzers.

Comparative study between bulk and surface modification on hy-drophobic membrane for dyeing and oily wastewater treatment

Surface modification could remarkably improve the oil–water separation ability of membrane, but suffers from limited survival positive effect layer after long-term operation. Herein, we report a systematic comparative study between bulk and surface modification (i.e., synchronous or sequential electrospun/elecrospraying) on hydrophobic polyvinylidene difluoride (PVDF) membrane. A hydrophilic UiO-66-NH2@polyacrylic acid micro/nanospheres (UiO@PAA) was selected as functional layer to improve the separation and adsorption capability of PVDF. The surface modification (SMM) and bulk modification membranes (BMM) exhibited the similar water wetting behavior in air as the same surface layer. The spider filament-like nanofibers of BMM could enhance the mechanical stability and dispersion uniformity of active sites among the PVDF fibers. In terms of oil-in-water emulsions separation ability, the BMM was superior to the SMM with the maximumly increase of separation efficiency and filtration flux to 1.3 % and 192.6 L m-2h−1, respectively. As for dye absorption, the BMM showed better adsorption capacity with a removal efficiency over 96 %. For the low concentration of methylene blue, the removal efficiency of SMM was only 94 %, while the removal efficiency of the BMM reached 98 % at room temperature. In addition, the BMM exhibited higher removal efficiency over 94 % compared with that less than 84 % of SMM after eight cycling tests, confirming its advantages in repeatability. This study demonstrates that the bulk modification can endow the initial membrane with better performance and durability, showing more promising prospects in actual wastewater treatment.

Engineering hydrophobicity and high-index planes of gold nanostructures for highly selective electrochemical CO2 reduction to CO and efficient CO2 capture

In current study, we demonstrate a strategy for improving the catalytic performance of gold (Au) for carbon dioxide reduction reaction (CO2RR), specifically enhancing selectivity for CO over hydrogen evolution reaction (HER) and increasing low-level CO2 capture efficiency. This involved controlling nanostructures without any further modification. Au nanostructures having four different morphologies (i.e., degree of roughness) were fabricated via electrodeposition at varied deposition potential, resulting in different intrinsic surface hydrophobicity and exposure of high-index planes depending on the actual morphology. The roughest Au, with its combination of the most hydrophobic feature and abundant high-index planes, generated greater partial current density (jCO) and faradaic efficiency for CO (FECO) than the other Au deposits within a tested potential region: The roughest Au showed 6-fold higher FECO (95.8 %) and 327-fold higher jCO (normalized to electrode geometric surface area) at −0.75 VRHE compared to the smoothest Au. Moreover, the roughest Au exhibited excellent CO2 capture ability even at low CO2 concentration, confirmed with scanning electrochemical microscopy. These improvement at hierarchical Au for CO2RR could be ascribed to two factors. Firstly, the morphology-driven hydrophobicity provides an optimal gas–liquid-solid triple-phase interfaces, increasing the local CO2 concentration near the Au catalyst surface due to its superb CO2 capture ability. Secondly, the abundant high-index planes serve as stable active sites for CO2RR, expediting the reaction rates. Remarkably, Au with the highest hydrophobicity and enriched high-index planes, even without any chemical modification, showed excellent CO2RR catalytic performance comparable to or even better than the other previously reported Au-based catalysts.

Confinement of CsPbBr3 Perovskite Nanocrystals into Extra‐large‐pore Zeolite for Efficient and Stable Photocatalytic Hydrogen Evolution

AbstractMetal halide perovskites (MHPs), renowned for their outstanding optoelectronic properties, hold significant promise as photocatalysts for hydrogen evolution reaction (HER). However, the low stability and insufficient exposure of catalytically active sites of bulky MHPs seriously impair their catalytic efficiency. Herein, we utilized an extra‐large‐pore zeolite ZEO‐1 (JZO) as a host to confine and stabilize the CsPbBr3 nanocrystals (3.4 nm) for boosting hydrogen iodide (HI) splitting. The as‐prepared CsPbBr3@ZEO‐1 featured sufficiently exposed active sites, superior stability in acidic media, along with intrinsic extra‐large pores of ZEO‐1 that were favorable for molecule/ion adsorption and diffusion. Most importantly, the unique nanoconfinement effect of ZEO‐1 led to the narrowing of the band gap of CsPbBr3, allowing for more efficient light utilization. As a result, the photocatalytic HER rate of the as‐prepared CsPbBr3@ZEO‐1 photocatalyst was increased to 1734 μmol ⋅ h−1 ⋅ g−1(CsPbBr3) under visible light irradiation compared with bulk CsPbBr3 (11 μmol ⋅ h−1 ⋅ g−1(CsPbBr3)), and the long‐term durability (36 h) can be achieved. Furthermore, Pt was incorporated with well‐dispersed CsPbBr3 nanocrystals into ZEO‐1, resulting in a significant enhancement in activity (4826 μmol ⋅ h−1 ⋅ g−1(CsPbBr3)), surpassing most of the Pt‐integrated perovskite‐based photocatalysts. Density functional theory (DFT) calculations and charge‐carrier dynamics investigation revealed that the dramatically boosted photocatalytic performance of Pt/CsPbBr3@ZEO‐1 could be attributed to the promotion of charge separation and transfer, as well as to the substantially lowered energy barrier for HER. This work highlights the advantage of extra‐large‐pore zeolites as the nanoscale platform to accommodate multiple photoactive components, opening up promising prospects in the design and exploitation of novel zeolite‐confined photocatalysts for energy harvesting and storage.

Highly efficient peroxymonosulfate activation by Fe[sbnd]Co bimetallic modified metal-organic frameworks-derived polyhedron with enriched oxygen vacancy for tetracycline degradation

It is important to propose a targeted solution strategy for the rate-limiting step in peroxymonosulfate activation in order to promote its wider application in advanced oxidation processes. In this study, a novel catalyst with FeCo bimetal doping, rich oxygen vacancy and porous polyhedral structure was prepared by using Fe, Co-doped Metal-Organic Framework as the precursor, which strategically enhanced the abundance and stability of active sites and promoted the adsorption of contaminates and PMS molecules. The M-450 (oxygen vacancy-rich)/PMS system demonstrated superior catalytic activity and interference resistance, in which 100 % of TC could be removed within 5 min. The corresponding reaction rate constant is 1.119 min−1, which is much higher than that of M-0 (without oxygen vacancy). Moreover, a series of studies proved that nonradical pathway (singlet oxygen) accompanied free radicals (sulfate radicals and hydroxyl radicals) collectively contributed to the tetracycline degradation. This study provides new ideas for the design and improvement of the functional catalyst for application in sulfate radicals based advanced oxidation processes.

Novel Nanostructured Pd/Co-Alumina Materials for the Catalytic Oxidation of Atmospheric Pollutants.

Cobalt-doped alumina catalysts were prepared using different methods, either conventional wet impregnation (WI) and/or advanced spray impregnation (SI), and they were evaluated as novel oxidation catalysts for CO and MeOH oxidation. The spray impregnation technique was used with the aim of achieving the synthesis of core-shell catalytic nanostructures to secure the chemical/thermal stability of active sites on the catalyst carrier. The catalysts were further promoted with a low Pd content (0.5 wt.%) incorporated via either incipient wetness impregnation (DI) or spray impregnation. The results revealed the superior performance of the spray-impregnated catalysts (Co/γ-Al2O3-SI) for both reactions. The deposition of Co oxide on the outer surface of the alumina particle (SEM images) and the availability of the active Co phase resulted in the enhancement of the Co/γ-Al2O3 catalysts' oxidation activity. Pd incorporation increased the catalysts' reducibility (TPR-H2) and improved the catalysts' performance for both reactions. However, the Pd incorporation method affected the catalytic performance; with the SI method, the active phase of Co3O4 was probably covered with PdO and was not available for the oxidation reactions. On the contrary, the incorporation of Pd with the DI method resulted in a better dispersion of PdO all over the Co/Al catalyst surface, maintaining available Co active sites and a better Pd-Co interaction. MeOH desorption studies revealed the methanol oxidation mechanism: the Co/Al catalysts promoted the partial oxidation of MeOH to formaldehyde (HCHO) and dehydration to dimethyl ether (DME), while the Pd-based Co/Al catalysts enhanced the complete oxidation of methanol to CO2 and H2O.

Construction of WS2/NC@C nanoflake composites as performance-enhanced anodes for sodium-ion batteries.

The development of layered metal sulfides with stable structure and accessible active sites is of great importance for sodium-ion batteries (SIBs). Herein, a simple liquid-mixing method is elaborately designed to immobilize WS2 nanoflakes on N-doped carbon (NC), then further coat carbon to produce WS2/NC@C. In the formation process of this composite, the presence of NC not only avoids the overlap and improves the dispersion of WS2 nanoflakes, but also creates a connection network for charge transfer, where the wrapped carbon provides a stable chemical and electrochemical reaction interface. Thus, the composite of WS2/NC@C exhibits the desired Na+ storage capacity as anticipated. The reversible capacity reaches the high value of 369.8 mA h g-1 at 0.2 A g-1 after 200 cycles, while excellent rate performances and cycle life are also acquired in that capacity values of 256.7 and 219.6 mA h g-1 at 1 and 5 A g-1 are preserved after 1000 cycles, respectively. In addition, the assembled sodium-ion hybrid capacitors (SIHCs, AC//WS2/NC@C) exhibit an energy/power density of 68 W h kg-1 at 64 W kg-1, and capacity retention of 82.9% at 1 A g-1 after 2000 cycles. The study provides insight into developing layered metal sulfides with eminent performance of Na+ storage.

Single-atom sites regulation by the second-shell doping for efficient electrochemical CO2 reduction

Nitrogen-doped carbon loaded single-atom catalysts (SACs) are promising candidates for electrocatalytic conversion of CO2 into high-valuable chemicals, and the modification of catalysts by heteroatom-doping strategy is an effective approach to enhance the CO2 reduction performance. However, the large difference exists in atomic radius between nitrogen atoms and the doped heteroatoms may lead to the poor stability of active sites. In this study, we have synthesized a Ni single atom catalyst with S doping at the second-shell on the ultrathin carbon nanosheets support (Ni-N4-SC) by solid-phase pyrolysis. The S atom in the second-shell contributes to the higher efficiency of CO2 conversion at lower potentials while the Ni-N4-SC can be more stable. The experimental results and theoretical calculations indicate that the S atom in second-shell breaks the uniform charge distribution and reduces the free energy of hydrogenation, which can increase the adsorption of CO2, accelerate charge transfer, and reduce the reaction energy barrier. This work reveals the close relationship between the second-shell and the electrocatalytic activity of single atom sites, which also provides a new perspective to design efficient single atom catalysts.

(Invited) Nucleation, Growth and Location Regulation of Heterogeneous Catalysts Synthesized by Atomic Layer Deposition

For supported catalysts, the particle surface or metal-support interface and its vicinity are the main areas providing active sites. In this regard, surface and interface engineering of heterogeneous catalysts is effective and critical for optimizing their catalytic performances. During the formation of active components, the structural uniformity, stability and location of nucleation sites determine the structural and scale uniformity, stability and environmental consistency of active sites, and ultimately determine their catalytic performance. Therefore, the regulation of nucleation, growth and location of active components is the key to precisely regulate the surface and interface structure and properties of supported catalysts. However, traditional preparation methods (such as impregnation method and precipitation method) have limitations in precise regulation of particle size, location and microstructure of catalysts due to the surface heterogeneity of supports and the high surface energy of nanoparticles, which makes it difficult to reliably reveal the structure-activity relationship of the catalyst. Therefore, the development of advanced fabrication methods is of vital significance to realize the nucleation, growth and location regulation of heterogeneous catalysts at atomic level precision. Atomic layer deposition (ALD) is a powerful scientific tool for catalytic research due to its self-limiting, atom-by-atom growth features. However, there is still a lack of rational knowledge of the nucleation and growth mechanism of catalytic particles prepared by ALD, the microscopic mechanism of interface structure modification, and the catalytic reaction mechanism. This is the topic of this lecture, in which we discuss the latest progress made in our group in precisely regulating the microstructure, size and location of ALD-deposited active components by several effective methods including nucleation site engineering, deposition kinetics engineering and template-assisted ALD method, as well as elucidating the nucleation and growth mechanism of ALD-deposited active components by in-situ and operando XAFS characterization based on our designed and built ALD-XAFS device. Through the above works, the nucleation and growth mechanisms of the deposited species and modification species, the microscopic mechanism of interface structure modification, and the influence of the size effect, the interface effect, and the distance effect on the catalytic performance were clarified. The structure-activity relationship was understood at the atomic/molecular level. These works will provide new ideas and scientific basis for the catalyst design and the performance regulation.

High-Entropy Alloys as Oxygen Reduction Reaction Electrocatalysts for Proton Exchange Membrane Fuel Cells Application

High entropy alloys (HEA) are complex multi-element materials. Owing to their multi-elemental nature, they can finetune surface adsorption energy and active sites which make them appealing to various catalytic reactions. HEI is a subclass of HEA that consist of an ordered alloy structure rather than a random alloy structure. The order-ness may induce more stable structures and uniform active sites, which in turn enhance the durability and activity under catalytic conditions. Here, we have synthesized a HEI(Pt40Ni20Co20Mn10Ir10) supported on porous carbon via a seed-mediated impregnation method. The intermetallic characteristics with periodic trends can be seen in the HAADF-STEM image (Fig. 1a). Based on the atomic arrangement, the HEI resembled a L12 structure. The corresponding EDX mapping the catalyst also showed the presence of all alloying species in the nanoparticles. The catalyst performance of the catalysts was evaluated in a 3-electrode liquid cell set-up with catalyst coated glassy carbon rotating disk electrode, Ag/AgCl and Pt mesh as working, reference and counter electrode, respectively. The catalyst’s mass activity (MA) was calculated based on the result obtained from ORR polarization test conducted under O2 saturated 0.1M HClO4. The initial mass activities for PtCo and HEA in ORR were 0.81 and 1.23 A mg-1 Pt, respectively (Fig. 1b), while that of Pt/C was only 0.26 A mg-1 Pt. A subsequent accelerated degradation test (ADT) was conducted under Ar-saturated 0.1M HClO4 with 0.6-1.0 V vs RHE square-wave cycling (3s hold at each potential) for 30k cycles. MA was measured after 10k and 30k cycles. HEA retained a MA of 0.48 A mg-1 Pt after the ADT, above the DOE target (0.44 A mg-1 Pt). We also compared our HEI samples synthesized with different annealing temperatures and duration (Fig. 1c), and it showed that 800◦C with 20 mins temperature hold showed the highest MA and electrochemical surface area (ECSA).Extended X-ray absorption spectroscopy (EXAFS) for the catalyst has also been conducted to further elucidate the structural-performance relationship of HEI (Fig.1d). From Pt L3 edge EXAFS fitting, the fitted R space showed that the Pt-Pt bond length was around 2.704 ± 0.004 Å, which was same as that of the PtCo (Fig. 1e). Therefore, it is believed that both HEI and PtCo has the same strain effect but HEI possessed stronger ligand effect than PtCo due to its unique Pt-M coordination, hence resulting in superior ORR performance over PtCo and Pt. Figure 1

Generating Multi-Carbon Products by Electrochemical CO2 Reduction via Catalytically Harmonious Ni/Cu Dual Active Sites.

Despite the unique advantages of single-atom catalysts, molecular dual-active sites facilitate the C-C coupling reaction for C2 products toward the CO2 reduction reaction (CO2RR). The Ni/Cu proximal dual-active site catalyst (Ni/Cu-PASC) is developed, which is a harmonic catalyst with dual-active sites, by simply mixing commercial Ni-phthalocyanine (Ni-Pc) and Cu-phthalocyanine (Cu-Pc) molecules physically. According to scanning transmission electron microscopy (STEM) and transmission electron microscopy (TEM) energy dispersive spectroscopy (EDS)data, Ni and Cu atoms are separated, creating dual-active sites for the CO2RR. The Ni/Cu-PASC generates ethanol with an FE of 55%. Conversely, Ni-Pc and Cu-Pc have only detected single-carbon products like CO and HCOO-. In situ X-ray absorption spectroscopy (XAS) indicates that CO generation is caused by the stable Ni active site's balanced electronic state. The CO production from Ni-Pc consistently increased the CO concentration over Cu sites attributed to subsequent reduction reaction through a C-C coupling on nearby Cu. The CO bound (HCOO-) peak, which can be found on Cu-Pc, vanishes on Ni/Cu-PASC, as shown by in situ fourier transformation infrared (FTIR). The characteristic intermediate of *CHO instead of HCOO- proves to be the prerequisite for multi-carbon products by electrochemical CO2RR. The work demonstrates that the harmonic dual-active sites in Ni/Cu-PASC can be readily available by the cascading proximal active Ni- and Cu-Pc sites.

Recent Advances of Covalent Organic Frameworks as Water Splitting Electrocatalysts

Developing high-performance, durable, yet low-lost catalysts for electrocatalytic water splitting technology has been a research priority to tackle the global energy crisis. In this regard, covalent organic frameworks (COFs) have received great attention as promising water splitting electrocatalysts as they can provide an excellent platform for the settlement of electrocatalytic active site, high porosity, and good stability. In this review, recent advances on the design and application of COFs for water electrolysis, which are hydrogen and oxygen evolution reaction electrocatalysts, are briefly discussed. Among them, both noble and non-noble metals containing COFs as well as metal-free COF-based electrocatalysts are elaborated. Furthermore, a brief outlook on the development of COFs in the field of water splitting electrocatalysis is provided.

Design of Superior Electrocatalysts for Proton-Exchange Membrane-Water Electrolyzers: Importance of Catalyst Stability and Evolution.

By virtue of the high energy conversion efficiency and compact facility, proton exchange membrane water electrolysis (PEMWE) is a promising green hydrogen production technology ready for commercial applications. However, catalyst stability is a challenging but often-ignored topic for the electrocatalyst design, which retards the device applications of many newly-developed electrocatalysts. By defining catalyst stability as the function of activity versus time, we ascribe the stability issue to the evolution of catalysts or catalyst layers during the water electrolysis. We trace the instability sources of electrocatalysts as the function versus time for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in acid and classify them into internal and external sources. Accordingly, we summarize the latest studies for stability improvements into five strategies, i. e., thermodynamic stable active site construction, precatalyst design, support regulation, superwetting electrode fabrication, and catalyst-ionomer interface engineering. With the help of ex-situ/ in-situ characterizations and theoretical calculations, an in-depth understanding of the instability sources benefits the rational development of highly active and stable HER/OER electrocatalysts for PEMWE applications.

Dry Reforming of Methane over Dual Metal Oxide Al2O3 + MOx (M = Ti, Zr, Si, Y) Supported Ni Catalyst: A Simple and Practical Approach

The complex catalyst synthesis procedure is always a hurdle in the industrialization of catalysts. Industry eagerly needs catalysts for the dry reforming of methane, which can be prepared through straightforward, cheap processes by semi-skilled workers. Herein, dual metal oxide support 10 wt% MOx (M = Ti, Si, Zr, Y) & 90 wt% Al2O3 is prepared by just mixing mechanically and thereafter, catalytic active 5 wt% Ni is dispersed over the support by impregnation method. Metal oxide pairs in ZrO2 + Al2O3, TiO2-Al2O3, SiO2 + Al2O3, and Y2O3 + Al2O3 supports are non-interacting, partially-interacting, significantly interacting (through Si–O–Al) and highly interacting (with maximum covalence character) respectively. Ni dispersed over SiO2 + Al2O3 or Y2O3 + Al2O3 supports are strongly interacted, whereas Ni/Y2O3 + Al2O3 catalyst has oxide enrichment over the surface for potential oxidation of carbon deposit. The interacting nature of metal oxide pair in support, stability of active sites and extent of oxide enrichment over the surface confirms the following order of coke deposition, Ni/Y2O3 + Al2O3 (8%) < Ni/SiO2 + Al2O3 (17%) < Ni/TiO2-Al2O3 (38.2%) < Ni/ZrO2 + Al2O3 (52.3%), as well as reverse order of catalytic activity, Ni/Y2O3 + Al2O3 (60%) > Ni/SiO2 + Al2O3 (55%) > Ni/TiO2-Al2O3 (50%) > Ni/ZrO2 + Al2O3 (47%).Graphical