Catalytic Performance Research Articles

Transition-Metal-Doped CeO2 for the Reverse Water-Gas Shift Reaction: An Experimental and Theoretical Study on CO2 Adsorption and Surface Vacancy Effects.

Transition metal-doped ceria (M-CeO2) catalysts (M = Fe, Co, Ni and Cu) with multiple loadings were experimentally investigated for reverse water gas shift (RWGS) reaction. Density functional theory (DFT) calculations were performed to benchmark the properties that impact catalytic activity of CO2 reduction. Temperature-programmed desorption (TPD) was conducted to study the CO2 binding strength on doped CeO2 surfaces; the trend of the energy along increasing metal loading agrees with the DFT calculations. Notably, CO2 dissociative adsorption energy and oxygen vacancy (OV) formation energy are key descriptors obtained from both DFT and experiments, which can be used to evaluate catalytic performance. Results show the effectiveness of transition metal doping in enhancing CO2 adsorption and reducibility of the surfaces, with Fe showing particularly promising results, i.e., CO2 conversion higher than 56% at 600 °C and 100% selectivity to CO. Cu exhibits 100% selectivity to CO but low CO2 conversion, while Co and Ni showed notable ability of methanation, particularly at high loadings. This study finds that an effective CeO2 based RWGS catalyst corresponds to OV sites that have low OV formation energies for surface reduction, and moderate CO2 adsorption energies for strong interaction with the surface to promote C-O bond scission.

Acid-base neutralization strategy for immobilization amino acid ionic liquid within sulfonic acid-based COF as a switch for selective conversion of epoxides

Covalent organic frameworks (COFs) and ionic liquids (ILs) as raw materials exhibit effective catalytic performance and adsorption capabilities in the reaction of epoxides and atmospheric CO2, respectively. Nonetheless, bonding modes between ILs and COFs have restricted their utility, thereby constraining the in-depth study of synergistic catalytic mechanisms over these composite catalysts. Herein, a heterogeneous composite ([DBUH]2Cys@COF-X) were successfully prepared by the facile acid-base neutralization method, incorporating varying amounts of amino acid ILs ([DBUH]2Cys) into the pore channels of sulfonic acid-based COF (TpPa-SO3H). [DBUH]2Cys@COF-3 efficiently catalyzed epichlorohydrin with a yield of 96.38 % without any solvent or co-catalyst under atmospheric CO2. Notably, larger sterically hindered epoxides were selectively blocked on the surface of [DBUH]2Cys@COF-3, enabling [DBUH]2Cys@COF-3 to act as a gatekeeper for selectively catalyzing small sterically hindered epoxides due to [DBUH]2Cys was distributed within the pore channels of [DBUH]2Cys@COF-3. Through DFT calculations, comprehensive understanding of the synergistic activation conferred of -COO- and [DBUH]+ towards CO2 and epoxides in [DBUH]2Cys@COF-3 and the ring-opening mechanism was clarified. This work presents a fresh outlook on the catalyst design by the facile acid-base neutralization method for efficiently catalyzing small-hindered epoxides under atmospheric CO2.

Synthesis of Chiral L2/Z-Type Ligands Featuring a Bis-Oxazoline Framework and their Application to Palladium-Catalyzed Asymmetric Allylic Alkylation

Chiral L2/Z*-type ligands featuring a bis-oxazoline framework have been successfully synthesized and applied in asymmetric allylic alkylation. These ligands, designed based on an oxazoline skeleton and derived from chiral amino acid derivatives, incorporate antimony and bismuth as Z-type ligands. Ligands with bulky, electron-withdrawing groups on antimony and bismuth showed enhanced catalytic performance. This research highlights the potential of these novel chiral L2/Z*-type ligands to improve asymmetric catalysis.

Antimony-assisted controlled growth of PtSe2 ribbon arrays for enhanced hydrogen evolution reaction

In this study, we report the successful synthesis of few-layer parallel PtSe2 ribbons on an Au foil employing a surface melting strategy via the chemical vapor deposition growth method at 650 °C. The controlled formation of parallel ribbons was directed by the Au steps generated through antimony treatment. These ribbons exhibit an average length of exceeding 100 μm and a width of approximately 100 nm across a substantial area. Electrocatalysis measurements showcase the catalytic performance of PtSe2 ribbons grown on Au foil, which can be further augmented through subsequent oxidation treatment. This investigation introduces an effective growth method for few-layer ribbons at low temperatures and broadens the scope of employing the substrate-guided strategies for the synthesis of one-dimensional materials. Additionally, it underscores the potential of PtSe2 ribbons as an electrocatalyst for hydrogen evolution.

Superior and efficient performance of cost-effective MIP-202 catalyst over UiO-66-(CO2H)2 in epoxide ring opening reactions

This study explored the catalytic performance of two robust zirconium-based metal–organic frameworks (MOFs), MIP-202(Zr) and UiO-66-(CO2H)2 in the ring-opening of epoxides using alcohols and amines as nucleophilic reagents. The MOFs were characterized by techniques such as FT-IR, PXRD, FE-SEM, and EDX. Through systematic optimization of key parameters (catalyst amount, time, temperature, solvent), MIP-202(Zr) achieved 99% styrene oxide conversion in 25 min with methanol at room temperature using 5 mg catalyst. In contrast, UiO-66-(CO2H)2 required drastically harsher conditions of 120 min, 60 °C, and four times the catalyst loading to reach 98% conversion. A similar trend was observed for ring-opening with aniline –MIP-202(Zr) gave 93% conversion in one hour at room temperature, while UiO-66-(CO2H)2 needed two hours at 60 °C for 95% conversion. The superior performance of MIP-202(Zr) likely stems from cooperative Brønsted/Lewis acid sites and higher proton conductivity enabling more efficient epoxide activation. Remarkably, MIP-202(Zr) maintained consistent activity over five recycles in the ring-opening of styrene oxide by methanol and over three recycles in the ring-opening of styrene oxide by aniline. Testing various epoxide substrates and nucleophiles revealed trends in reactivity governed by electronic and steric effects. The results provide useful insights into tuning Zr-MOF-based catalysts and highlight the promise of the cost-effective and sustainable MIP-202(Zr) for diverse epoxide ring-opening reactions on an industrial scale.

Enhanced catalytic performance and antichlorine poisoning over Cu-doped cobalt oxide nanosheets for chlorobenzene oxidation

The degradation of Chlorinated volatile organic compounds (CVOCs) by catalytic oxidation forms toxic products, and catalysts may be poisoned by chlorine at low temperatures. To address this, a Cu-assisted strategy is proposed for enhancing the catalytic degradation of chlorobenzene (CB) over cobalt oxide nanosheets. The Cu-doped Co3O4 catalysts exhibited lower T90 values (temperatures with 90 % conversion) and improved stability compared to the unmodified catalyst. These results were attributed to strong metal-metal interactions between Cu species and cobalt oxide nanosheets, which showed a high specific surface area, reduced binding energy of lattice oxygen, higher surface oxygen concentration, and more surface Co3+ species. These properties promoted low-temperature catalytic activity. In addition, the disappearance of Cu2+ satellite peak after the catalyst is used, indicating that the Cu2+ also contributes to the catalytic activity. Furthermore, the in situ FTIR spectra provided details about the reaction mechanism of CB degradation over Cu-doped cobalt oxide nanosheets. The oxygen vacancy generation and the surface absorption of chlorine-containing intermediates were calculated using density functional theory calculations. This study provides new insight into novel pathways for catalyst design aimed at CB degradation.

Unraveling the effect and difference of S or Si atoms modified Pd-based catalysts in tuning catalytic performance of C2H2 semi-hydrogenation

Modifying the spatial scale of active site has been proven a good strategy for enhancing catalytic performance. In this study, the Pd-based catalysts with different spatial scale of active site were constructed via the modification of non-metallic S or Si atoms over Pd, Cu alloyed Pd SACs, PdAg surface alloy and PdM (M=Au, Ag) IMCs catalysts, then, C2H2 semi-hydrogenation catalytic performance was identified based on DFT calculations. The findings indicate that the catalytic performance of C2H2 semi-hydrogenation is greatly influenced by the spatial extent of active site and the electronic effect modified by the S or Si atoms. Geometric effect caused by S or Si atoms reduces the spatial scale of active site over S/Pd-2 × 2, Si/Pd-3 × 3, S/Pd6Ag, S/Pd1Au1, S/Pd1Ag1 and Si/Pd1Ag1, thereby preventing green oil generation. Electronic effect caused by S or Si atoms leads to far away from the Fermi level of d-band center over S/Pd-2 × 2, Si/Pd-3 × 3, S/Pd1Au1, S/Pd1Ag1 and Si/Pd1Ag1 to improve C2H4 production activity and selectivity. Seven catalysts S/Pd-2 × 2, Si/Pd-3 × 3, PdCu-2 × 2, S/Pd6Ag, S/Pd1Au1, S/Pd1Ag1 and Si/Pd1Ag1 are screened out to present high selectivity and activity of C2H4 production, and effectively prevent green oil generation. This study provides valuable structural insights for designing high-performance catalysts by the modification of non-metallic atom in C2H2 semi-hydrogenation.

Optimizing the Intermediates Adsorption by Manipulating the Second Coordination Shell of Ir Single Atoms for Efficient Water Oxidation

The precise regulation of single‐atom catalysts (SACs) with the desired local chemical environment is vital to elucidate the relationship between the SACs structure and the catalytic performance. The debate on the effect of the local coordination environment is quite complicated even for the SACs with the same composition and chemical nature, calling for increased attention on the regulation of second coordination shell. For oxide‐supported SACs, it remains a significant challenge to precisely manipulate the second coordination shell of single atoms supported on oxides due to the structural robustness of oxides. Here, Ir single atoms are anchored on NiO supports via different bonding strategies, resulting in the diverse Ir‐O‐Ni coordination numbers for Ir sites. Specifically, Ir1/NiO, Ir1‐NiO, and Ir1@NiO SACs with increasing Ir‐O‐Ni coordination numbers of 3, 4, and 5 were synthesized, respectively. We found that the activity of the three samples towards oxygen evolution reaction (OER) exhibited a volcano‐shaped relationship with the Ir‐O‐Ni coordination number, with Ir1‐NiO showing the lowest overpotential of 225 mV at 10 mA cm‐2. Mechanism investigations indicate that the moderate coordination number of Ir‐O‐Ni in Ir1‐NiO creates the higher occupied Ir dz2 orbital, weakening the adsorption strength for *OOH intermediates and thereby enhancing the OER activity.

Enhanced Fenton Degradation of Tetracycline over Cerium-Doped MIL88-A/g-C3N4: Catalytic Performance and Mechanism

Since enormous amounts of antibiotics are consumed daily by millions of patients all over the world, tons of pharmaceutical residuals reach aquatic bodies. Accordingly, our study adopted the Fenton catalytic degradation approach to conquer such detrimental pollutants. (Ce0.33Fe) MIL-88A was fabricated by the hydrothermal method; then, it was supported on the surface of g-C3N4 sheets using the post-synthetic approach to yield a heterogeneous Fenton-like (Ce0.33Fe) MIL-88A/10%g-C3N4 catalyst for degrading the tetracycline hydrochloride drug. The physicochemical characteristics of the catalyst were analyzed using FT-IR, SEM-EDX, XRD, BET, SEM, and XPS. The pH level, the H2O2 concentration, the reaction temperature, the catalyst dose, and the initial TC concentration were all examined as influencing factors of TC degradation efficiency. Approximately 92.44% of the TC was degraded within 100 min under optimal conditions: pH = 7, catalyst dosage = 0.01 g, H2O2 concentration = 100 mg/L, temperature = 25 °C, and TC concentration = 50 mg/L. It is noteworthy that the practical outcomes revealed how the Fenton-like process and adsorption work together. The degradation data were well-inspected by first-order and second-order models to define the reaction rate. The synergistic interaction between the (Ce0.33Fe) MIL-88A/10%g-C3N4 components produces a continuous redox cycle of two active metal species and the electron-rich source of g-C3N4. The quenching test demonstrates that •OH is the primary active species for degrading TC in the H2O2–(Ce0.33Fe) MIL-88A/10%g-C3N4 system. The GC-MS spectrum elucidates the yielded intermediates from degrading the TC molecules.

Optimizing the Intermediates Adsorption by Manipulating the Second Coordination Shell of Ir Single Atoms for Efficient Water Oxidation.

The precise regulation of single-atom catalysts (SACs) with the desired local chemical environment is vital to elucidate the relationship between the SACs structure and the catalytic performance. The debate on the effect of the local coordination environment is quite complicated even for the SACs with the same composition and chemical nature, calling for increased attention on the regulation of second coordination shell. For oxide-supported SACs, it remains a significant challenge to precisely manipulate the second coordination shell of single atoms supported on oxides due to the structural robustness of oxides. Here, Ir single atoms are anchored on NiO supports via different bonding strategies, resulting in the diverse Ir-O-Ni coordination numbers for Ir sites. Specifically, Ir1/NiO, Ir1-NiO, and Ir1@NiO SACs with increasing Ir-O-Ni coordination numbers of 3, 4, and 5 were synthesized, respectively. We found that the activity of the three samples towards oxygen evolution reaction (OER) exhibited a volcano-shaped relationship with the Ir-O-Ni coordination number, with Ir1-NiO showing the lowest overpotential of 225 mV at 10 mA cm-2. Mechanism investigations indicate that the moderate coordination number of Ir-O-Ni in Ir1-NiO creates the higher occupied Ir dz2 orbital, weakening the adsorption strength for *OOH intermediates and thereby enhancing the OER activity.

Temperature-Sensitive Template for Preparation of ZnO/CeO2 Composite Photocatalytic Materials and Its Catalytic Performance

In this work, a series of thermosensitive ionic liquid functionalized polymers, PNx(IL)y, with controllable morphology and particle size were prepared by free radical polymerization. Then, using the polymer PN64(IL)8 with uniform morphology as a templating agent, the ZnO composite photocatalytic materials doped with rare earth metal Ce were prepared in combination with a microwave-assisted and templated hydrothermal reaction method. Series different Ce-doping amount photocatalytic materials ZnO-Ce-x‰ were characterized by XRD, SEM, TEM, XPS, and other methods. The results demonstrated that the templated materials PN64(IL)8 can prepare ZnO-Ce-2‰ with uniform petaloid ambulacra shape, good distribution of elements, and excellent photocatalytic performance. Photocatalytic degradation experiments of methyl orange (MO) showed that when the Ce-doping amount is only 2‰, the degradation rate of organic dyes can reach 96.5% by reacting the photocatalytic materials in water for 1 h. In addition, this kind of photocatalyst can be used for the degradation of high-concentration MO, as well as being easily recovered and effectively reused by simple filtration. Therefore, the structure of this kind of photocatalyst is controllable in the preparation process with an extremely low Ce-doping amount compared with current reports, and it has a good application prospect in the field of wastewater treatment technology.

Stability of Nitrogen-Doped Activated Carbon as an Electrocatalyst for the Oxygen Reduction Reaction in Various Storage Media

Besides outstanding catalytic performance, the stability of nitrogen-doped carbon materials during storage is equally crucial for practical applications. Therefore, we conducted the first investigation into the stability of highly nitrogen-doped activated carbon (AC-NC-T) obtained by modifying activated carbon with CO2/NH3 in different storage media (air, vacuum and N2). The results of the catalysis of the oxygen reduction reaction and the activation of peroxymonosulfate for degrading bisphenol A by AC-NC-T show that the catalytic activity of AC-NC-T stored in air decays most prominently, while the performance attenuated only marginally when stored in vacuum and N2. The results from N2 adsorption isotherms, Raman spectroscopy, elemental and X-ray photoelectron spectroscopy indicate that the decline in catalytic activity is due to the presence of oxygen in the environment, causing a decrease in absolute contents of pyridinic N (N-6) and graphitic nitrogen (N-Q). After being stored in an air atmosphere for 28 days, the absolute contents of N-6 and N-Q in AC-NC-950 decreased by 19.3% and 12.1%, respectively. However, when stored in a vacuum or N2, the reduction in both was less than 7%. This study demonstrates that reducing oxygen concentration during storage is crucial for preserving high catalytic activity of nitrogen-containing carbon materials.

Enhanced Low‐Temperature Oxidation Activity of Cu‐Doped Highly Active Pd‐Based Catalysts

Pd‐based catalysts supported on cerium‐zirconium (CZ) oxygen storage materials (OSM) have emerged as promising candidates for the catalytic oxidation of CH4 and CO. However, achieving efficient and stable treatment of CH4 and CO in exhaust gases with Pd‐based catalysts remains a long‐term challenge. To address this, we propose a straightforward strategy of doping the supports with Cu to enhance the catalytic performance of Pd/Ce0.4Zr0.5La0.1O1.95 catalysts. Performance tests revealed that the catalytic activity of the Cu‐doped catalysts significantly improved, with T90 (CH4) decreasing from 418 to 301 ℃ and T90 (CO) decreasing from 141 to 113 ℃. Notably, the copper‐doped catalysts exhibited enhanced water and sulfur resistance while maintaining excellent thermal stability. The CO conversion decreased by less than 2% after a thermal deactivation experiment lasting over 100 hours. The reduction in particle size and the increase in specific surface area due to copper doping are key factors contributing to the improved total oxygen storage capacity (OSC). The main reasons for the increase in total OSC are likely the reduced particle size and increased specific surface area.

Co-MoS2@BC catalyzed ultrafast degradation of tetracycline by peroxymonosulfate: Domination of non-radical pathway based on 1O2

Co-MoS2@BC catalysts were prepared using pine cones as biochar source, and the surface morphology and microstructure of the catalysts were analyzed and the successful preparation of the materials was verified by adopting the characterization means such as BET, SEM, XRD, FTIR, TEM, XPS, Raman. At the concentration of tetracycline (TC) in water of 20 mg/L, the reaction system with catalyst participation resulted in 98.88 % pollutant removal and efficient degradation, and the effects of TC concentration, coexisting chemicals, initial pH, catalyst dosage, PMS dosage, and other factors on the catalytic performance of Co-MoS2@BC were investigated. The results of quenching experiments and electron paramagnetic resonance (EPR) examinations were combined, the reactive substances whose main roles in the reaction process were identified as single linear oxygen (1O2), and the simultaneous presence of electron transfer-mediated non-radical pathways in the Co-MoS2@BC/PMS/TC system was confirmed using Linear sweep voltammetry (LSV). The reaction process's intermediates were examined using liquid chromatography-mass spectrometry (LC-MS), which also offered potential degradation routes.

Nickel nanocatalyst on lanthanum aluminate: Optimizing preparation and evaluating performance in glycerol dry reforming for syngas production

In this study, mesoporous nanocrystalline Ni/La-Al catalysts with varying nickel (Ni) loadings (5, 10, 15, and 20 wt.%) were synthesized using a solid-state method for the glycerol dry reforming (GDR) reaction. The effects of different Ni loadings and the addition of steam on the structural and catalytic performance of the catalysts were investigated. Characterization techniques, including Brunauer-Emmett-Teller (BET) surface area analysis, temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), and X-ray diffraction (XRD) were employed to analyze the catalysts' properties. Results showed that increasing Ni loading to 10 wt.% improves the catalytic properties. However, by increasing the Ni loading, a decrease in catalytic properties due to increasing particle size, creating NiO bulk phase and surface pore blockage is obvious. A series of experiments were performed to investigate the effect of steam usage on catalytic properties. TPO analysis revealed that steam addition reduces the carbon deposition and shifts oxidation peaks to lower temperatures; consequently, the activity and stability of the catalyst will be enhanced. Although the 5 - 7.5 vol.% of steam in the feed composition significantly stabilizes the catalyst, it is possible to produce H2-rich synthesis gas, and conversely, increasing the temperature reduces the H2/CO ratio. Various examinations were conducted under different conditions, including varying gas hourly space velocity (GHSV), carbon-to-glycerol ratio (CGR), and temperature, to obtain more comprehensive data on the catalysts.

Unveiling the Enhancement of Electrocatalytic Oxygen Evolution Activity in Ru-Fe2O3/CoS Heterojunction Catalysts.

The development of highly efficient electrocatalysts for the sluggish anodic oxygen evolution reaction (OER) is crucial to meet the practical demand for water splitting. In this study, an effective approach is proposed that simultaneously enhances interfacial interaction and catalytic activity bymodifyingFe2O3/CoS heterojunctionusing Ru doping strategy to construct an efficient electrocatalytic oxygen evolution catalyst. The unique morphology of Ru doped Fe2O3 (Ru-Fe2O3) nanoring decorated by CoS nanoparticles ensures a large active surface area and a high number of active sites. The designed Ru-Fe2O3/CoS catalyst achieves a low OER overpotential (264mV) at 10mAcm-2 and demonstrates exceptional stability even at high current density of 100mAcm-2, maintaining its performance for an impressive duration of 90h. The catalytic performance of this Ru-Fe2O3/CoS catalyst surpasses that of other iron-based oxide catalysts and even outperforms the state-of-the-art RuO2. Density functional theory (DFT) calculation as well as experimental in situ characterization confirm that the introduction of Ru atoms can enhance the interfacial electron interaction, accelerating the electron transfer, and serve as highly active sites reducing the energy barrier for rate determination step. This work provides an efficient strategy to reveal the enhancement of electrocatalytic oxygen evolution activity of heterojunction catalysts by doping engineering.

Cobalt-Modified Biochar from Rape Straw as Persulfate Activator for Degradation of Antibiotic Metronidazole

A cobalt-loaded magnetic biochar (Co-MBC) catalyst was synthesized to enhance the removal of metronidazole (MNZ). Study explored the performance and mechanism of MNZ degradation by Co-MBC activated permonosulfate (PMS). Results showed that cobalt oxides were effectively deposited onto the biochar surface, new oxygen functional groups were added to the modified biochar, and the presence of the metallic element Co enhanced the efficiency of PMS activation in the composite. More than 90% of MNZ was removed after 60 min with a catalyst dosage of 0.2 g/L and a PS concentration of 1 mM. After four reuses, Co-MBC still showed excellent catalytic performance to degrade over 75% of MNZ. The reaction system performed well even in the presence of inorganic anions and organic macromolecules. However, the degradation rate was inhibited under alkaline conditions. The quenching experiment indicated that •SO4−, •OH, 1O2, and •O2− synergistically degraded MNZ, and that•SO4− played a dominant role. LC-MS was applied to assess intermediate degradation products, in which CO2, H2O, and NO3− were the final degradation products, and potential degradation pathways were suggested. In conclusion, Co-MBC was an efficient and stable catalytic material, and its ability to activate PMS was improved to effectively degrade antibiotics, a typical priority pollutant.

Tailoring Cu-SiO2 Interaction through Nanocatalyst Architecture to Assemble Surface Sites for Furfural Aqueous-Phase Hydrogenation to Cycloketones.

In this contribution, nanocatalysts with rather diverse architectures were designed to promote different intimacy degrees between Cu and SiO2 and consequently tune distinct Cu-SiO2 interactions. Previously synthesized copper nanoparticles were deposited onto SiO2 (NPCu/SiO2) in contrast to ordinarily prepared supported Cu/SiO2. NPCu@SiO2 and SiO2@Cu core-shell nanocatalysts were also synthesized, and they were all bulk and surface characterized by XRD, TGA, TEM/HRTEM, H2-TPR, XANES, and XPS. It was found that Cu0 is the main copper phase in NPCu/SiO2 while Cu2+ rules the ordinary Cu/SiO2 catalyst, and Cu0 and electron-deficient Cuδ+ species coexist in the core-shell nanocatalysts as a consequence of a deeper metal-support interaction. Catalytic performance could not be associated with the physical properties of the nanocatalysts derived from their architectures but was associated with the more refined chemical characteristics tuned by their design. Cu/SiO2 and NPCu/SiO2 catalysts led to the formation of furfuryl alcohol, evidencing that catalysts holding weak or no metal-support interaction have no significant impact on product distribution even in the aqueous phase. The establishment of such interactions through advanced catalyst architecture, allowing the formation of electron-deficient Cuδ+ moieties, particularly Cu2+ and Cu+ as unveiled by spectroscopic investigations, is critical to promoting the hydrogenation-ring rearrangement cascade mechanism leading to cycloketones.

NiSX/carbon black hybrids for efficient electrochemical oxidation of 5-hydroxymethyfurfural to 2,5-furandicarboxylic acid

NiSX stands out in the electrochemical oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) due to the favorable conductivity and diverse chemical composition. However, NiSX usually exhibits few exposed active sites and poor charge transfer kinetics. Moreover, during the electrochemical oxidation of HMF, the conductivity of the catalyst would decrease rapidly with the formation of oxidized Ni species, leading to a rapid decline in catalytic performance. Therefore, a series of NiSX/carbon black (CB) hybrids (NiSX/CB-n) were synthesized via a one-step solvent hydrothermal method in which NiSX displayed a large cubic block structure assembled from small nanosheets. Among the prepared catalysts, NiSX/CB-2, with the optimal amount of introduced CB, exhibited superior electrocatalytic activity for the oxidation of HMF, achieving 100% HMF conversion, 98% FDCA yield, and 100% Faradaic efficiency at 1.45 V (vs. RHE). The outstanding electrocatalytic activity of NiSX/CB-2 was attributed to the suitable CB doping, which not only enhanced the conductivity of catalyst but also separated the small nanosheets, preventing the formation of densely packed NiSX structure and increasing the specific surface area of catalyst, thereby exposing more active sites and improving the availability of material. Furthermore, the formation of C-S bonds facilitated charge interactions between NiSX and CB, promoting the transfer of charges during the electrolysis process and enhancing electrocatalytic kinetics. Open circuit potential tests demonstrated that the introduction of CB also strengthened the adsorption capacity of catalyst for HMF, further benefiting its electrocatalytic activity.

Insight into the role of droplets in quinoa starch-based Pickering high internal phase emulsion for enzymatic hydrolysis reaction

Pickering high internal phase emulsion has emerged as potential platforms for biocatalytic reactions. Herein, native quinoa starch was used as the emulsifier to form a stable Pickering HIPE with an internal phase up to 80 %. The catalytic performance of lipase loaded in HIPE was evaluated for the enzymatic hydrolysis of hexyl hexanoate. Compared with the typical Pickering emulsion, biphasic, and monophasic systems, the Pickering HIPE system displayed higher conversion (83.54 % at 1440 min) and specific enzyme activity (1.41 U/mg), thus emphasizing the crucial role of microdroplets and large interface area created by both the starch particles and high internal phase volume. Subsequently, HIPEs with different starch concentrations were fabricated to further understand the catalysis behavior happening at compartmentalized microdroplets and interfaces. The microstructural, interfacial, and rheological properties of the HIPEs were systematically determined to explain the correlation between emulsion properties and catalytic efficiency. High starch concentration reduced the droplet size and increased the interfacial area, thus shortening the mass transfer distance and enlarging the reaction area. Meanwhile, the increased surface coverage and viscosity led to poor accessibility and limited mass movement. This trade-off made the maximum conversion be obtained at 2 wt% concentration. The study provides novel information about the role of emulsion droplets in the catalytic performance of lipase in starch-based HIPE.