High Catalytic Activity Research Articles

Efficient Atomically Dispersed Co/N-C Catalysts for Formic Acid Dehydrogenation and Transfer Hydrodeoxygenation of Vanillin.

Atomically dispersed catalysts have gained considerable attention due to their unique properties and high efficiency in various catalytic reactions. Herein, a series of Co/N-doped carbon (N-C) catalysts was prepared using a metal-lignin coordination strategy and employed in formic acid dehydrogenation (FAD) and hydrodeoxygenation (HDO) of vanillin. The atomically dispersed Co/N-C catalysts showed outstanding activity, acid resistance, and long-term stability in FAD. The improved activity and stability may be attributed to the high dispersion of Co species, increased surface area, and strong Co-N interactions. XPS and XAS characterization revealed the formation of Co-N3 centers, which are assumed to be the active sites. In addition, DFT calculations demonstrated that the adsorption of formic acid on single-atom Co was stronger than that on Co13 clusters, which may explain the high catalytic activity. The Co/N-C catalyst also showed promising performance in the transfer HDO of vanillin with formic acid, without any external additional molecular H2.

Photosynthetic microalgae microbial fuel cells for bioelectricity generation and microalgae lipid recovery using Gd-Co@N-CSs/NF as cathode

Photosynthetic microalgae microbial fuel cells (PMMFCs) have an enormous potential for wastewater treatment and bioenergy recovery. However, to overcome low power generation problem, it is crucial to understand how the operational parameters influence the pathways and mechanisms of PMMFCs performance. In this study, microalgae (Chlorella vulgaris, Chlorella sp., Tetradesmus obliquus and Microcystis aeruginosa), light intensity (1400, 2100 and 3200 lx) and light/dark cycle (12/12, 18/6 and 24/0) were screened to promote the bioenergy recovery of PMMFCs. The highest power generation and electrochemical activity were obtained for Chlorella vulgaris under 3200 lx and cycle 18/6, with the maximum power density of 2.0 W m−3, and the lowest charge transfer resistance of 26.60 Ω and Tafel slope of 44.74 mV dec−1. Correlation analysis showed a significant negative correlation between NH4+-N concentration in the cathode chamber and output voltage. Structural equation model further elucidated that NH4+-N indirectly regulated the output voltage via the negative association with dissolved oxygen. In addition, the by-product lipid reached 145 mg g−1 dry mass. Furthermore, the specific gravity, iodine value, and cetane number of the fatty acids met the production standards for biodiesel. The electroactive bacteria Propionibacteriaceae (24.45%) were the dominant genera. This study provided suitable microalgae species and crucial operating conditions for bioenergy recovery from electrochemical systems with high catalytic activity.

A Family of Hexacopper Phenylsilsesquioxane/Acetate Complexes: Synthesis, Solvent-Controlled Cage Structures, and Catalytic Activity.

Convenient self-assembly synthesis of copper(II) complexes via double (phenylsilsesquioxane and acetate) ligation allows to isolate a family of impressive sandwich-like cage compounds. An intriguing feature of these complexes is the difference in the structure of a pair of silsesquioxane ligands despite identical (Cu6) nuclearity and number (four) of acetate fragments. Formation of particular combination of silsesquioxane ligands (cyclic/cyclic vs condensed/condensed vs cyclic/condensed) was found to be dependent on the synthesis/crystallization media. A combination of Si4-cyclic and Si6-condensed silsesquioxane ligands is a brand new feature of cage metallasilsesquioxanes. A representative Cu6-complex (4) (with cyclic silsesquioxanes) exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. Maximum yield of the products of cyclohexane oxidation attained 30 %. The compound 4 was also tested as catalyst in the Baeyer-Villiger oxidation of cyclohexanone by m-chloroperoxybenzoic acid: maximum yields of 88 % and 100 % of ϵ-caprolactone were achieved upon conventional heating at 50 °C for 4 h and MW irradiation at 70 or 80 °C during 30 min, respectively. It was also possible to obtain the lactone (up to 16 % yield) directly from the cyclohexane via a tandem oxidation/Baeyer-Villiger oxidation reaction using the same oxidant.

A dual modification strategy of highly active catalytic cathode for proton-conducting solid oxide fuel cell with Ni-doped PrBaFe1.9Mo0.1O6-δ

The cathode catalytic activity and stability in a temperature range of 550–700 °C is crucial to the development of proton-conductive solid oxide fuel cells (PCFCs). A facile dual-modification strategy is developed for the design of Ni-doped PrBaFe1.9Mo0.1O6-δ (PBFMN), composed of a major perovskite and a minor NiO phases, as a cobalt-free cathode. The composite cathode PBFMN exhibits high catalytic activity and stability. Computational simulation indicates that the perovskite phase increases the oxygen vacancies and enhances the proton transfer, while nickel oxide nanoparticles improve oxygen adsorption and dissociation. The fuel cell with as-prepared PBFMN reached a peak power density 1.23 W cm−2 at 700 °C. The improved performance of the cell is mainly due to the fast ORR kinetics. This work provides a new insight into the design of cobalt-free cathode for a PCFC.

Sustainable energy generation: High-performance NiCo2S4@S-g-C3N4 bifunctional electrocatalyst advances water splitting efficiency

Efforts to create cost-effective electrocatalysts from abundant materials, for the utilization of water electrolysis reactions, are viewed as promising sources for sustainable clean energy generation. This article describes the synthesis of cobalt sulphide (CoS) nanoparticles using a straightforward and environmentally friendly one-pot hydrothermal process. The series of nickel-doped CoS (NiCo2-x S4) introduced with varying the weight percentage of Ni (1, 2, 4, 8, 6, and 10 wt%), and the composite Ni-dopped CoS on varying the weight percentage (10, 30, 50, 70, and 90 wt %) of sulfur-doped graphitic carbon nitride (NiCo2S4@S-g-C3N4) was created. Utilizing X-ray diffraction analysis (XRD), EDS, FTIR, and scanning electron microscopy (SEM) synthesized electrocatalysts were characterized. Doped with Fluorine After being changed with an electrocatalyst, tin oxide was used as the working electrode to monitor the electrochemical activity of the whole water splitting process using chronopotentiometry, cyclic voltammetry (CV), linear sweep voltammetry (LSV), and EIS. NiCo2S4@S-g-C3N4 exhibited higher electrocatalytic performance with an overpotential 370 mV for OER and 415 mV for HER at the current intensity of 10 mAcm−2. Transition metal sulfide electrocatalysts exhibit good electrolytic performance, due to their high surface areas and intrinsically high catalytic activity. These findings suggest that the NiCo2S4@S-g-C3N4 composite possesses a significant role for use in energy conversion and energy storage applications.

Significantly improved dehydrogenation of dodecyl-N-ethylcarbazole over supported PdFe bimetallic nanocatalysts via polydopamine surface modification of Al2O3

N-ethylcarbazole (NEC) has great application prospects in hydrogen storage due to its ability to dehydrogenate at lower energy and high hydrogen storage performance. Developing supported metal catalysts with high catalytic activity and stability is key to achieving large-scale application of LOHC hydrogen storage technology. In this paper, bimetallic FePd/Al2O3@PDA-GR catalysts used for the dehydrogenation process of 12H-NEC were prepared by stepwise reduction methods, including chemical reduction and galvanic replacement, using PDA-coated Al2O3 as the support. The characterization results showed that adding PDA could anchor the metal particles, improve the dispersion of metal particles on the support surface, and reduce the agglomeration phenomenon. The nanoparticles of bimetallic catalysts prepared by the galvanic replacement were small, with the particle size distribution of 0.86 nm-2.78 nm, and an average size of 1.52 nm. The large number of exposed active sites enabled the catalysts to reduce the dosage of Pd while still possessing excellent catalytic performance. And part of Pd was coated on Fe NPs in the Fe5Pd1/Al2O3@PDA-GR catalysts prepared by galvanic replacement, which improved the atom utilization of Pd. And there is an obvious electronic interaction between Fe and Pd. In the dehydrogenation process of 12H-NEC to NEC, The prepared FePd/Al2O3@PDA-GR catalyst exhibited excellent catalytic performance and had a significantly greater dehydrogenation efficiency than found in the literature, 95% for 1 h and 100% for 3 h at 180 °C. The temperature drop to 160 °C did not affect the dehydrogenation efficiency, which remained at 98.1% for 3 h. The prepared catalyst had good stability, and the dehydrogenation efficiency was 93.1% after five successive cycles.

Structural Evolution of GaOx-Shell and Intermetallic Phases in Ga-Pt Supported Catalytically Active Liquid Metal Solutions.

We present a comprehensive scale-bridging characterization approach for supported catalytically active liquid metal solutions (SCALMS) which combines lab-based X-ray microscopy, nano X-ray computed tomography (nano-CT), and correlative analytical transmission electron microscopy. SCALMS catalysts consist of low-melting alloy particles and have demonstrated high catalytic activity, selectivity, and long-term stability in propane dehydrogenation (PDH). We established an identical-location nano-CT workflow which allows us to reveal site-specific changes of Ga-Pt SCALMS before and after PDH. These observations are complemented by analytical transmission electron microscopy investigations providing information on the structure, chemical composition, and phase distribution of individual SCALMS particles. Key findings of this combined microscopic approach include (i) structural evolution of the SCALMS particles' GaOx shell, (ii) Pt segregation toward the oxide shell leading to the formation of Ga-Pt intermetallic phases, and (iii) cracking of the oxide shell accompanied by the release of liquid Ga-Pt toward the porous support.

3D monolithic composites TiO2/HKUST-1/RGO@melamine foam with improved surface mass transfer for efficient photocatalytic degradation of toluene gas

Currently, photocatalytic technology mostly uses powdered TiO2 catalysts, which are not conducive to recycling, limit the contact between volatile organic compounds (VOCs) and the photocatalyst, and result in lower mass transfer efficiency in gas-solid reactions. Meanwhile, TiO2 catalysts including the electrospun TiO2 nanofibers with hydrophilic surfaces are not favorable for the infiltration and adsorption of non-polar VOCs. To solve these problems, in this work, the monolithic composites TiO2/HKUST-1/RGO@melamine foam (named MRTH) with improved surface mass transfer composed of metal-organic framework (HKUST-1), graphene oxide (GO) and electrospun TiO2 nanofibers was designed. The metal-organic framework HKUST-1 plays a role in promoting the adsorption of toluene, while the reduced graphene oxide (RGO) facilitates the infiltration of non-polar molecules on the surface of the composite and has better electron transport capability. A type II heterojunction between the electrospun TiO2 nanofibers and HKUST-1 formed in the monolithic composites suppresses the recombination of electron-hole pairs and extends their lifespan. Comparing with the bare electrospun TiO2 nanofibers, the MRTH foam composites exhibit a wider light absorption range, hydrophilic and oleophobic properties and a higher separation efficiency of photogenerated carriers. In 90 min of dark adsorption, the removal rate of toluene over MRTH-8 was 52.32 %, while under irradiation by xenon lamp for 150 min, the removal rate over MRTH-8 reached 90.15 %. The amount of monolithic foam composites can also be easily adjusted in the reactor to achieve the best possible removal of the contaminant. The prepared composite materials have been characterized in detail, and the possible mechanisms have also been discussed. The foam composites prepared in this work have high catalytic activity and gas-solid reaction mass transfer efficiency, so they have wide practical application prospects in the field of VOCs abatement.

Poly(ionic liquid)-based aerogels for continuous-flow CO2 upcycling

The atmospheric concentration of CO2 is rising at an alarming pace, creating a pressing need for new and sustainable materials capable of capture and conversion. Poly(ionic liquid)s (PILs) are particularly effective catalysts for processes at or near atmospheric pressure. PILs industrial application poses challenges due to the low porosity of PIL, the limited batch conversion capacity, and the difficulties in reuse. To overcome these limitations, we herein propose the use of AEROPILs catalysts obtained from the integration of PILs in chitosan-based aerogels. These cost-effective highly porous materials have unique and tuneable porous properties making them not only ideal sustainable CO2 sorbents but also promising heterogeneous catalysts. While AEROPILs show moderate yields for CO2 conversion in batch mode, high catalytic activity was achieved when AEROPILs were used to catalyse the CO2 cycloaddition reaction to epoxides in packed-bed reactors operated under continuous flow. The catalytic activity and stability were maintained over 60 h without activity loss, and high productivity (space-time yield of 21.18 gprod h−1 L−1). This research reveals the pioneering use of AEROPILs to efficiently upcycle CO2 into cyclic carbonate under a continuous flow setup.

A heterostructured ternary transition metal oxide composite as an efficient electrocatalyst for the hydrogen evolution reaction

A key method for hydrogen production is water electrolysis involving the oxygen and hydrogen evolution reactions. The efficiency of these processes is largely dependent on the use of effective electrode catalysts. Despite the high water-splitting catalytic activity of noble metals such as Pt, Ru, and Ir, their scarcity and costliness pose significant challenges. Although Fe and Fe-based compounds have recently been identified as promising alternative catalysts due to their abundance, affordability, and low toxicity, particularly under the alkaline conditions required for the hydrogen evolution reaction, both can be reduced to unstable forms during the reaction. To address this, the focus of the present study is on developing a ternary transition metal oxide electrocatalyst comprising Ni, Fe, and Co oxides. Thereby, we leveraged the synergistic interactions among them to provide a heterogeneous electrocatalyst for the hydrogen evolution reaction with a sufficiently low overpotential of 45 mV and suitably high Tafel kinetics of 44.99 mV dec−1 and long-term stability. The ternary transition metal oxide electrode showcased superior performance compared to one comprising binary transition metal oxides by achieving a lower overpotential and a better Tafel slope while maintaining catalytic stability even for 100 h at a current density of 1000 mA cm−2. This innovative approach offers a highly efficient alternative catalyst to Fe, which is known to have stability issues for hydrogen production, especially at high current density.

Tuning Photoredox Catalysis of Ruthenium with Palladium: Synthesis of Heterobimetallic Ru-Pd Complexes That Enable Efficient Photochemical Reduction of CO2.

New Ru-Pd heterobimetallic complexes were synthesized and structurally characterized utilizing 6,6″-bis(phosphino)-2,2':6',2″-terpyridine as a scaffold for the metal-metal bond. The dicationic Ru-Pd complex was found to exhibit high catalytic activity as a photocatalyst for photochemical reduction of CO2 to CO under visible light irradiation. This study established a new design of transition metal catalysts that tune photoredox catalysis with metalloligands.

Embedded metal inducing electron accumulation of multi-mesoporous pyridinic-N doped carbon for enhancing *COOH adsorption in electrochemical CO2 reduction

Nitrogen-doped carbon (NC) for carbon dioxide reduction reaction (CO2RR) are promising candidates. However, its selectivity and activity are limited by the undeveloped pore and limited electronic effect. Herein, we propose a strategy of three birds with one stone to utilize the embedded nickel for inducing electron-rich pyridinic-NC with multimodal porous structure based on the hard template assisted sacrificial template method. Nickel acts as sacrificial agent and inducer to facilitate the formation of mesoporous and reactive nitrogen species for capturing and activating reactants, respectively. Besides, we find that nickel as electron donor endows the NC with electron accumulation for participating actively in PCET reaction. The resultant Ni0.87-NC-1-AE exhibits an eminent FECO of 97.6 % with excellent activity and stability. In-situ Raman spectroscopy and the projected crystal orbital Hamilton populations (pCOHP) confirm the accumulation of *COOH and the stable adsorption of *COOH on the surface. What’s more, the well-designed experiments and DFT calculations accurately locate pyridinic-N as the active site, where the aggregated electrons donated by nickel significantly reduce the energy barrier of rate-determining step and promote the desorption of CO. This work provides an instructive perspective to construct advanced NC electrocatalysts with high mass transfer efficiency and high catalytic activity.

Long‐Term Stability of Ammonia Decomposition over Nickel‐Based Catalysts

Green hydrogen can be used as the backbone of a novel energy system and as a feedstock for renewable chemistry. H2 storage and transport are challenging, but ammonia as a hydrogen carrier could potentially solve these inefficiencies. Many studies focus on high catalytic activities, but the long‐term stability is often insufficiently investigated. This work reports on the stability of a nickel‐based reference catalyst and a coprecipitated Ni/Al2O3 catalyst over 800 h time on stream (TOS) in 98% NH3 at atmospheric pressure. An automated temperature control is necessary to adjust the temperature of the heat source to compensate for the changing heat demand resulting from catalyst activation or deactivation. Under reaction conditions the reference catalyst first undergo an activation phase before reaching its maximum conversion of 91.9% after 250 h TOS followed by a minor decrease in conversion. In comparison, the Ni/Al2O3 catalyst shows lower activity and undergo a continuous deactivation due to sintering. Overall, the activity loss at 534 °C amounted to only 1.5% for the reference catalyst and to 13.5% for the Ni/Al2O3 catalyst compared with the maximum conversion level. Thus, the Ni‐based reference catalyst proves to be very stable under industrially relevant NH3 decomposition conditions.

Dual‐Shelled Hollow Leafy Carbon Support with Atomically Dispersed (N,S)‐Bridged Hydroxy‐Coordinated Asymmetric Fe Sites for Oxygen Reduction

AbstractSingle‐atom catalysts (SACs) are widely studied in various chemical transformations due to their high catalytic activity and atom utilization. However, modulating the catalytic performance of catalysts by adjusting the microenvironment remains a great challenge. In this paper, a novel master‐double guest vulcanization‐assisted strategy is reported for synthesizing Fe single‐atom catalysts on N,S codoped porous hollow leaf carbon (FeSA/N,S‐PHLC) with highly exposed FeN3SOH sites. Fe(mIm) (guest I) is loaded on the surface of ZIF‐L (host) and then trithiocyanuric acid (TCA, guest II) is bonded with Fe(mIm), and the resulting ZIF‐L@Fe(mIm)@TCA precursors can be converted to FeSA/N,S‐PHLC with controllable structures. In addition, XPS analysis yield an increase in pyridine N content in FeSA/N,S‐PHLC compared to FeSA/N‐PHLC. It can be demonstrated by theoretical calculations that the N,S‐coordinated axially hydroxy‐coordinated asymmetric Fe centers synergistically with the abundance of pyridinic nitrogen facilitate the adsorption and desorption of oxygen intermediates, and the 3d orbitals of the Fe active centers can be optimized. The prepared FeSA/N,S‐PHLC catalyst has a half‐wave potential (E1/2) of 0.91 V under alkaline conditions, and E1/2 = 0.75 V under acidic conditions. It shows excellent cycle stability (882 h) and power density (217 mW cm−2) in the assembly of zinc–air battery (ZABs) devices.

Self-Supported WO3@RuO2 Nanowires for Electrocatalytic Acidic Water Oxidation.

Developing catalysts with high catalytic activity and stability in acidic media is crucial for advancing hydrogen production in proton exchange membrane water electrolyzers (PEMWEs). To this end, a self-supported WO3@RuO2 nanowire structure was grown in situ on a titanium mesh using hydrothermal and ion-exchange methods. Despite a Ru loading of only 0.098 wt %, it achieves an overpotential of 246 mV for the oxygen evolution reaction (OER) at a current density of 10 mA·cm-2 in acidic 0.5 M H2SO4 while maintaining excellent stability over 50 h, much better than that of the commercial RuO2. After the establishment of the WO3@RuO2 heterostructure, a reduced overpotential of the rate-determining step from M-O* to M-OOH* is confirmed by the DFT calculation. Meanwhile, its enhanced OER kinetics are also greatly improved by this self-supported system in the absence of the organic binder, leading to a reduced interface resistance between active sites and electrolytes. This work presents a promising approach to minimize the use of noble metals for large-scale PEMWE applications.

Spontaneous built-in electric field in heterostructure electrocatalysts with high catalytic activity and conductivity: Inducing 3D nucleation of Li2S

Lithium-sulfur (Li-S) batteries have become a research focus due to their high theoretical specific capacity and energy density. The shuttle effect and slow sulfur conversion kinetics of lithium polysulfides (LiPSs) severely hindered their practical application. Here, a N-doped carbon nanofiber self-supporting electrode modified with cobalt selenide/nickel selenide as a sulfur carrier (CoSe2/NiSe2@NCNFs) is designed and constructed. The experimental results show that a built-in electric field is formed at the interface of CoSe2/NiSe2 Mott-Schottky heterostructure, which promotes the conversion of LiPSs and induces 3D nucleation of Li2S. Furthermore, the calculation results of density functional theory clearly reveal high conductivity, adsorption and interfacial charge transfer between CoSe2/NiSe2 Mott-Schottky heterostructure electrocatalyst and LiPSs. As a result, the CoSe2/NiSe2@NCNFs/S cathode shows a specific capacity of 1050.8 mAh g−1 at 1 C, and maintains excellent cycling performance with a discharge capacity of 735.1 mAh g−1 and a capacity decay of 0.003 % per cycle over 1000 cycles. This work designed a Mott-Schottky heterostructure electrocatalyst to strengthen the adsorption and conversion of LiPSs and induce 3D nucleation of Li2S, providing a new idea for high-performance Li-S batteries.

Organocatalytic ring-opening polymerization of lactide by bis(thiourea) H-bonding donating cocatalysts with binaphthyl-amine framework

Development of H-bonding organo-catalysts with high catalytic activity and high degree of control is significantly important for the metal-free polyesters that are potentially suitable for biomedical usage. The concomitant use of base and commercially available thiourea generally suffered from prolonged reaction time and resulted in incomplete monomer conversion in some cases. Introducing one or more (thio)urea H-bonding donating arms to the parent thiourea has been proved to be an effective method for substantially increasing the activity of thiourea H-bonding donors. Consequently, we synthesized bis-thioureas derived from binaphthyl-amine bearing different substituents and investigated their catalytic performance in ROPs of lactide in this work. The density functional theory (DFT) calculations suggested that the “activated-thiourea” mode is more preferred for the bis(thiourea) containing binaphthyl-amine framework. The bis(thiourea)/base binary systems could effectively promote the LA polymerization using benzyl alcohol as initiator. The polymerization rates and the degree of control over the polymerization are highly dependent on the structures of the bis(thiourea) and base. Bis(thiourea)/1,5,7-triazabicyclo[4.4.0]dec‑5-ene pairs exhibited highest catalytic activity compared to other bis(thiourea)/base pairs, and the turnover frequency is high up to 1980 h–1 at 75 °C. In addition, the bulky hindrance and axial chirality of the binaphthyl-amine framework could enable stereoselective ROP of rac-LA to produce isotactic-rich and crystalline PLAs at relatively low temperature (0 °C). Mechanistic studies indicated that both enantiomorphic site control (ESC) and chain end control (CEC) concurrently occurred in the rac-LA polymerization catalyzed by bis(thiourea)/base binary systems. This work will inspire future design of H-bonding donors with high catalytic performance.

Development and performance of NLISA for C-reactive protein detection based on Prussian blue nanoparticle conjugates.

Prussian blue nanoparticles (PBNPs), also called nanozymes, are very attractive as an alternative to horseradish peroxidase in immunoassay development due to their simple and low-cost synthesis, stability and high catalytic activity. Today, there is a method for highly effective PBNP synthesis based on the reduction of an FeCl3/K3[Fe(CN)6] mixture by hydrogen peroxide. However, there is a lack of research showcasing the use of these highly effective PBNPs for specific target detection in clinical settings, as well as a lack of comprehensive comparisons with conventional methods. To address this gap, we prepared diagnostic reagents based on highly effective PBNPs by modifying them using gelatin and attaching anti-C-reactive protein (CRP) monoclonal antibodies through cross-linking with glutaraldehyde. As a result, a solid-phase colorimetric immunoassay in a sandwich format (nanozyme-linked immunosorbent assay [NLISA]) using highly effective PBNPs as a label for CRP detection has been demonstrated for the first time. The assay demonstrated a detection limit of 21.8pg/mL, along with acceptable selectivity, precision (CV < 25%) and accuracy (the recovery index was within acceptable limits (75-125%) for LLOQ /ULOQ range. The analytical performance of this method is on par with sensitive assays developed in the last 5 years. Notably, the results obtained from NLISA align with those from an immunofluorescence assay conducted by a certified clinical laboratory. Furthermore, this study underscores the technological challenges involved in constructing an analysis that necessitate further exploration.

Highly Active and Sintering-Resistant Pt Clusters Supported on FeOx-Hydroxyapatite Achieved by Tailoring Strong Metal-Support Interactions.

The catalytic performance of supported metal catalysts is closely related to their structure. While Pt-based catalysts are widely used in many catalytic reactions because of their exceptional intrinsic activity, they tend to deactivate in high-temperature reactions, requiring a tedious and expensive regeneration process. The strong metal-support interaction (SMSI) is a promising strategy to improve the stability of supported metal nanoparticles, but often at the price of the activity due to either the coverage of the active sites by support overlay and/or the too-strong metal-support bonding. Herein, we newly constructed a supported Pt cluster catalyst by introducing FeOx into hydroxyapatite (HAP) support to fine-tune the SMSIs. The catalyst exhibited not only high catalytic activity but also sintering resistance, without deactivation in a 100 h test for catalytic CO oxidation. Detailed characterizations reveal that FeOx introduced into HAP weaken the strong covalent metal-support interaction (CMSI) between Pt and FeOx while simultaneously inhibiting the oxidative strong metal-support interaction (OMSI) between Pt and HAP, giving rise to both high activity and thermal stability of the supported Pt clusters.

Gel-casting of mesoporous silica electrolyte membranes loaded with phosphoric acid for protonic electrolyte cells

Proton conducting membranes that operate at temperatures above 100 °C are highly sought after for use in energy devices such as fuel cells owing to the high catalytic activity of electrodes induced by elevated temperature and no requirement for water management. In the present study, novel mesoporous silica membranes were prepared by a gel-casting process using commercial colloidal silica and subsequent sintering. These membranes served as the scaffold for phosphoric acid-based electrolytes. Well-interconnected mesopores with uniform pore sizes was effective for hosting phosphoric acid (PA), and the tunable pore sizes (5.9–32.0 nm) were achieved by tuning the sintering temperature from 500 to 725 °C. High porosity (about 50%) and high hydrophilicity of silica membranes are beneficial to reach high phosphoric acid loading by an impregnation process. The PA-loaded membrane sintered at 700 °C achieved a high protonic conductivity of 0.11 S cm−1 and a peak power density of 287.3 mW cm−2 in hydrogen fuel cells at 160 °C. The conductivity is 1 order of magnitude higher than that of the pressed meso-silica membranes and comparable to that of PA-mesoporous silica spheres. This study has demonstrated a new method to construct high-temperature protonic electrolyte membranes.