Hybrid Catalyst Research Articles

Interface reconstruction of NiCoP@NiMoP self-supported electrodes for highly efficient alkaline water/seawater electrolysis

Electrocatalytic water splitting is considered a feasible hydrogen generation technique. However, their sluggish kinetics and poor stability remains a huge challenge for alkaline water electrolysis. Herein, we report a corrosion-resistant NiCoP@NiMoP micro-pillar arrays for catalysts. It indicates that a layer of amorphous film on the surface of catalysts exposes many active sites and accelerates the species reconstruction. The prepared hybrid catalysts present an overpotential of 76 mV at −10 mA cm−2 for hydrogen evolution reaction (HER) and 268 mV@100 mA cm−2 for oxygen evolution reaction (OER). Furthermore, the assembled cell realizes a stable and high-efficiency water splitting with cycling life of 100 h in seawater media. This work provides a universal approach toward highly active and durable electrocatalysts.

Bridging Dehydrogenation and Hydrogenation in Heterogeneous Catalysis: A Demonstration of a Unified Catalytic Approach.

In the pursuit of enhancing the applications of hydrogen as an energy carrier, this research delved into the utilization of a singular hybrid catalyst capable of performing both dehydrogenation and hydrogenation processes for Liquid Organic Hydrogen Carriers (LOHCs). This study presents the synthesis and characterization of a hybrid catalyst, combining an organometallic pincer complex with Pd-Ru heterostructures supported on γ-alumina. Unlike conventional transition and noble metal nanoparticles, the use of a pincer complex offers exceptional thermal stability due to its aryl backbone, which is advantageous for various endothermic dehydrogenation reactions of hydrocarbons in LOHCs. This pioneering hybrid catalyst is a novel approach, demonstrating a proof of concept. In this study, we utilized the hybrid catalyst to investigate the dehydrogenation and hydrogenation of a lower enthalpic system, specifically the cyclooctane-cyclooctene system. The dehydrogenation of cyclooctane was conducted at 443 K using tertiary butyl ethylene as a sacrificial hydrogen acceptor, while the hydrogenation of cyclooctene reaction catalyzed by Pd-Ru nanostructures occurred at 298 K and 1 atm H2. The results showed successful tandem dehydrogenation-hydrogenation reactions. However, challenges were noted in terms of catalytic activity and recyclability, providing valuable insights for further refinement and optimization.

Green Synthesis of the Triazine Derivatives and their Application for the Benign Electrocatalytic Reaction of Nitrate Reduction to Ammonia.

This work uses green sustainable reactions twice. Firstly, it is microwave synthesis: 2,4,6-tribiphenyl-4-yl-1,3,5-triazine and similar compounds were prepared in a closed microwave reactor in n-octane by the Friedel-Crafts reaction. Second, a hybrid electrocatalyst for the highly demanded electrochemical reaction of nitrate reduction to ammonia (NO3RR) was prepared based on this material. This reaction has great potential to replace the energy-intensive Haber-Bosch process, and in addition, has independent value for the elimination of nitrate contamination of water resources. As shown in the work, microwave synthesis is an eco-friendly method for the synthesis of complex organic compounds; fast, selective and with a high yield of the target product. The electrocatalyst deposited on the graphite electrode consisted of a layer of 2,4-bis([1,1'-biphenyl]-4-yl)-6-hydroxy-1,3,5-triazine and related compounds coated with cobalt oxide. The hybrid catalyst was firmly retained on the graphite electrode during NO3RR and the material showed impressive stability with almost no decrease in catalytic activity even after the fifth cycle. Both 2,4-bis([1,1'-biphenyl]-4-yl)-6-hydroxy-1,3,5-triazine and the catalyst based on this substance were characterized by SEM, XPS, XRD, UV-vis spectra, cyclic (and linear) voltammetry, and chronoamperometry. This work can serve as a starting point for the development of stable and durable electrocatalysts for NO3RR using triazine derivatives.

Efficient Silver(I)‐Containing I–Motif DNA Hybrid Catalyst for Enantioselective Diels–Alder Reactions

AbstractThe inherent chiral structures of DNA serve as attractive scaffolds to construct DNA hybrid catalysts for valuable enantioselective transformations. Duplex and G‐quadruplex DNA‐based enantioselective catalysis has made great progress, yet novel design strategies of DNA hybrid catalysts are highly demanding and atomistic analysis of active centers is still challenging. DNA i‐motif structures could be finely tuned by different cytosine‐cytosine base pairs, providing a new platform to design DNA catalysts. Herein, we found that a human telomeric i‐motif DNA containing cytosine‐silver(I)‐cytosine (C‐Ag+‐C) base pairs interacting with Cu(II) ions (i‐motif DNA(Ag+)/Cu2+) could catalyze Diels–Alder reactions with full conversions and up to 95 % enantiomeric excess. As characterized by various physicochemical techniques, the presence of Ag+ is proved to replace the protons in hemiprotonated cytosine‐cytosine (C : C+) base pairs and stabilize the DNA i‐motif to allow the acceptance of Cu(II) ions. The i‐motif DNA(Ag+)/Cu2+ catalyst shows about 8‐fold rate acceleration compared with DNA and Cu2+. Based on DNA mutation experiments, thermodynamic studies and density function theory calculations, the catalytic center of Cu(II) ion is proposed to be located in a specific loop region via binding to one nitrogen‐7 atom of an unpaired adenine and two phosphate‐oxygen atoms from nearby deoxythymidine monophosphate and deoxyadenosine monophosphate, respectively.

Efficient Silver(I)-Containing I-Motif DNA Hybrid Catalyst for Enantioselective Diels-Alder Reactions.

The inherent chiral structures of DNA serve as attractive scaffolds to construct DNA hybrid catalysts for valuable enantioselective transformations. Duplex and G-quadruplex DNA-based enantioselective catalysis has made great progress, yet novel design strategies of DNA hybrid catalysts are highly demanding and atomistic analysis of active centers is still challenging. DNA i-motif structures could be finely tuned by different cytosine-cytosine base pairs, providing a new platform to design DNA catalysts. Herein, we found that a human telomeric i-motif DNA containing cytosine-silver(I)-cytosine (C-Ag+-C) base pairs interacting with Cu(II) ions (i-motif DNA(Ag+)/Cu2+) could catalyze Diels-Alder reactions with full conversions and up to 95 % enantiomeric excess. As characterized by various physicochemical techniques, the presence of Ag+ is proved to replace the protons in hemiprotonated cytosine-cytosine (C : C+) base pairs and stabilize the DNA i-motif to allow the acceptance of Cu(II) ions. The i-motif DNA(Ag+)/Cu2+ catalyst shows about 8-fold rate acceleration compared with DNA and Cu2+. Based on DNA mutation experiments, thermodynamic studies and density function theory calculations, the catalytic center of Cu(II) ion is proposed to be located in a specific loop region via binding to one nitrogen-7 atom of an unpaired adenine and two phosphate-oxygen atoms from nearby deoxythymidine monophosphate and deoxyadenosine monophosphate, respectively.

CoFe2O4@N‐CNH as Bifunctional Hybrid Catalysts for Rechargeable Zinc‐Air Batteries

AbstractImproving the efficiency of bifunctional electrocatalysts is a decisive challenge in the area of long‐lasting rechargeable zinc‐air batteries. Enhancing the catalysts' performance is crucial for advancing zinc‐air batteries. Transition‐metal oxides have emerged as promising non‐precious, noble‐metal‐free catalysts. Herein, a unique precursor directed approach is introduced for preparing a cobalt ferrite@nitrogen doped carbon nanohorns (CoFe2O4@N‐CNHs) nanohybrid catalyst in a single step annealing process involving stoichiometric amounts of single‐source cobalt and iron molecular precursors and carbon nanohorns (CNHs) under an argon/ammonia (Ar/NH3) atmosphere. This procedure enables a simultaneous CoFe2O4 ferrite synthesis and nitrogen functionalization of CNHs. The precious metal free nanohybrid CoFe2O4@N‐CNHs‐30% containing 30% of carbon presents an oxygen reduction reaction (ORR) half wave potential and onset potential comparable to the standard ORR catalyst 20% Pt/C. CoFe2O4@N‐CNHs‐30% also establishes superior oxygen evolution reaction (OER) performance with a low overpotential and a small Tafel slope than benchmark OER catalyst RuO2. Furthermore, the rechargeable zinc‐air battery with the CoFe2O4@N‐CNHs‐30% nanohybrid as air electrode demonstrates steadier and more durable charge–discharge cycles, and outstanding energy density relative to the state‐of‐the‐art 20% Pt/C‐RuO2 catalyst.

Ti-doped synergistic hollow thin-walled Bi2O3 nano-microspheres for efficient tetracycline hydrochloride photodegradation

Bismuth oxide (Bi2O3) has been extensively investigated in the fields of environmental photocatalysis, owing to its exceptional charge transport performance and remarkable resistance to photocorrosion. However, the limited absorption spectrum of light and rapid recombination of photogenerated charge results in a low quantum efficiency. Herein, an efficient photocatalytic system for tetracycline hydrochloride (TCH) photodegradation based on titanium (Ti)-doped hollow, thin-walled Bi2O3 with nano-microspheres is fabricated via a facile self-assembly strategy. It is shown that doping Ti in Bi2O3 can generate oxygen vacancies, in addition, the addition of Ti in the solvothermal process inhibits the conversion of Bi3+ to bismuth at high temperature, making the content of each component in the heterostructure controllable. The hybrid catalyst exhibits superior performance in visible-light-driven photocatalytic degradation of TCH (about 95.1 % degradation efficiency after 120 min) and excellent stability (up to 4 cycles) under visible light irradiation. The optimized catalyst exhibits excellent performance in visible light catalytic degradation, owing to the synergistic effect of high specific surface area, Bi plasma resonance effect and charge mobility. Moreover, the photocatalytic mechanism of Ti-Bi2O3 have been deeply analyzed through experimental investigation and DFT theoretical calculations. The findings contribute to the synthesis of efficient visible-light-driven Bi-based photocatalysts and to the understanding of photocatalytic degradation reactions.

One-Pot Phyto-Mediated Synthesis of Fe2O3/Fe3O4 Binary Mixed Nanocomposite Efficiently Applied in Wastewater Remediation by Photo-Fenton Reaction

A binary Fe2O3/Fe3O4 mixed nanocomposite was prepared by phyto-mediated avenue to be suited in the photo-Fenton photodegradation of methylene blue (MB) in the presence of H2O2. XRD and SEM analyses illustrated that Fe2O3 nanoparticles of average crystallite size 8.43 nm were successfully mixed with plate-like aggregates of Fe3O4 with a 15.1 nm average crystallite size. Moreover, SEM images showed a porous morphology for the binary Fe2O3/Fe3O4 mixed nanocomposite that is favorable for a photocatalyst. EDX and elemental mapping showed intense iron and oxygen peaks, confirming composite purity and symmetrical distribution. FTIR analysis displayed the distinct Fe-O assignments. Moreover, the isotherm of the developed nanocomposite showed slit-shaped pores in loose particulates within plate-like aggregates and a mesoporous pore-size distribution. Thermal gravimetric analysis (TGA) indicated the high thermal stability of the prepared Fe2O3/Fe3O4 binary nanocomposite. The optical properties illustrated a narrowing in the band gab (Eg = 2.92 eV) that enabled considerable absorption in the visible region of solar light. Suiting the developed binary Fe2O3/Fe3O4 nanocomposite in the photo-Fenton reaction along with H2O2 supplied higher productivity of active oxidizing species and accordingly a higher degradation efficacy of MB. The solar-driven photodegradation reactions were conducted and the estimated rate constants were 0.002, 0.0047, and 0.0143 min−1 when using the Fe2O3/Fe3O4 nanocomposite, pure H2O2, and the Fe2O3/Fe3O4/H2O2 hybrid catalyst, respectively. Therefore, suiting the developed binary Fe2O3/Fe3O4 nanocomposite and H2O2 in photo-Fenton reaction supplied higher productivity of active oxidizing species and accordingly a higher degradation efficacy of MB. After being subjected to four photo-Fenton degradation cycles, the Fe2O3/Fe3O4 nanocomposite catalyst still functioned admirably. Further evaluation of Fe2O3/Fe3O4 nanocomposite in photocatalytic remediation of contaminated water using a mixture of MB and pyronine Y (PY) dyestuffs revealed substantial dye photodegradation efficiencies.

Diols production from pyrolysis oil water‐soluble fraction

AbstractBACKGROUNDThe production of value‐added chemicals from pyrolysis oil or its fractions is of great significance for the valorization of biomass. Diols, including ethylene glycol (EG) and 1,2‐propylene glycol (1,2‐PG), are important bulk chemicals with widespread industrial applications. Here we investigated the production of diols from pyrolysis oil water‐soluble fraction (WS) using a hybrid catalyst (Ni + H2WO4).RESULTSFirstly, levoglucosan, glycolaldehyde and acetol, three main components in WS, were respectively selected as the single model compound, and their respective conversions into diols were investigated at different temperatures for different reaction times. The result showed the optimum reaction temperature and time were 180 °C and 2 h respectively, under which a EG yield of 53.8% and 1,2‐PG yield of 5.2% were obtained from levoglucosan conversion, a EG yield of 98.6% was obtained from glycolaldehyde conversion, and a 1,2‐PG yield of 98.5% was obtained from acetol conversion. The reaction pathway of levoglucosan conversion was analyzed. Secondly, the model mixture of levoglucosan, glycolaldehyde and acetol was used to simulate the real WS, and their conversion was investigated at different ratios of H2WO4 to Ni. The result showed the optimum catalyst composition was 0.15 g H2WO4 and 0.3 g Ni, under which a EG yield of 76.4% and 1,2‐PG yield of 38.4% were obtained. Thirdly, the real original WS was converted under the optimum reaction conditions and the result only gave a EG yield of 19.1% and 1,2‐PG yield of 25.8% (based on the carbon moles of main substrates), which were much less than the two yields of model mixture. That was related to the presences of other types of chemicals in original WS. After the original WS being adsorbed by activated carbon, the yields of EG and 1,2‐PG could be increased to 39.2% and 37.9%, respectively.CONCLUSIONThe presences of certain other types of chemicals (such as acids, furans, phenolics and cyclopentanones) in original WS inhibited the production of diols. The activated carbon adsorption could efficiently remove most of furans, phenolics and cyclopentanones in original WS and increased significantly the diols yields. © 2024 Society of Chemical Industry (SCI).

Optimizing Light Dynamics: Designing a Ni-MOF Functionalized g-C3N4 Type II Heterostructure and a Ti3C2 MXene Schottky Junction for the Efficient Photocatalytic H2 Production.

The photocatalytic production of hydrogen (H2) from water is a vital avenue towards sustainable energy and addressing global environmental challenges. To maximize efficiency, harnessing the synergistic effects of multiple co-catalysts is essential, as these interactions can significantly enhance performance. In this study, we introduce a ternary heterojunction composed of a nickel-imidazole framework (Ni-MOF), graphitic carbon nitride (CN), and Ti3C2 MXene (TC), employing solvothermal and wet impregnation methods, featuring a well-designed Type II heterojunction and a noble metal-free Schottky junction for efficient hydrogen evolution. The Type II heterojunction between Ni-MOF and CN minimizes charge carrier recombination and promotes photogenerated electron generation, while TC as an electron acceptor enhances electron capture, increases participation in surface reactions, and augments active sites. Consequently, the Ni-MOF/CN/TC hybrid catalyst achieves outstanding photocatalytic hydrogen evolution under visible light, with a peak production rate of 1044.46 μmol/g over 3 hours, surpassing CN by 13 fold and Ni-MOF/CN by 50 %. This work provides insights into MXene-based ternary systems, emphasizing the potential for enhanced light absorption and efficient charge separation, making it a promising platform for photocatalytic applications.

Hybrid Catalysts in Photoredox Arylation of Sodium Arylsulfinates

Hybrid Catalysts in Photoredox Arylation of Sodium Arylsulfinates

Low-Temperature Catalytic Transfer Hydrogenation of Biomass-Derived Furfural over Irreversibly Adsorbed and Highly Dispersed Zr(IV) Species.

Developing pure inorganic catalysts for low-energy transfer hydrogenation of biomass-derived furfural and alcohols below 100 °C is still challenging. This work reports highly dispersed Zr(IV) species catalysts prepared by irreversible adsorption of different solvent-dissolved Zr(IV) cations such as Zr4+ or [Zr4(OH)8(H2O)16]8+ on/in SBA-15 through Zr-O coordination, without adding an alkaline precipitant and calcination treatment. In the transfer hydrogenation of furfural to furfuryl alcohol, the Zr(IV) species catalysts exhibited unexpectedly outstanding transfer hydrogenation activity at low temperatures of 70 and 85 °C, superior to other transition-metal (Zr4+, Hf4+, Fe3+, etc.)- and main-group metal (Al3+, etc.)-based inorganic catalysts, which need high reaction temperatures above 100 °C, and comparable to the best-performing metal-organic hybrid catalysts with precise defect engineering modification or specific macromolecular ligands, and had negligible Zr leaching amounts (<0.01%) in water and in the collected liquid reaction medium from 7 cycles of reactions. In addition, the large strong Lewis acidic site amount rather than the large total acidic amount is a crucial condition for the catalysts to obtain high transfer hydrogenation activity, and basic sites were also involved in catalysis, and their absence would induce the acetalization side reaction. Furthermore, the catalysts were universal for low-temperature transfer hydrogenation of other aldehydes.

Evaluation of photocatalytic properties of TiO2/g-C3N4 core-shell hybrid catalyst supported on Sr4Al14O25:eu,dy phosphor

TiO2/g-C3N4 hybrid compounds were supported as core-shell catalyst on Sr4Al14O25:Eu,Dy phosphor powder by a 2-step hydrothermal and solvothermal self-assembly method. Surface and chemical characterizations confirmed that the phosphor substrate and the hybrid catalysts co-existed as a multi-composite material. Where nano spherical TiO2 particles were dominant as core/shell catalyst. Diffuse reflectance spectra were shifted toward the visible light region (400 nm to 600 nm) in composites with g-C3N4 as shell-catalyst. X-ray photon spectroscopy (XPS) confirmed the chemical integrity and binding of g-C3N4 on phosphor/TiO2 material. When g-C3N4 was coated as shell-catalyst on phosphor/TiO2, superior photocatalytic performances of above 90% efficiency were obtained in comparison to where TiO2 was coated as shell-catalyst under both ultraviolet and visible light illumination. Thus, g-C3N4 is more active as shell-catalyst owing to its lower band gap of 2.7 eV than core TiO2 (3.2 eV).

Effect of TiO2 on Acidity and Dispersion of H3PW12O40 in Bifunctional Cu-ZnO(Al)-H3PW12O40/TiO2 Catalysts for Direct Dimethyl Ether Synthesis

The performance of bifunctional hybrid catalysts based on phosphotungstic acid (H3PW12O40, HPW) supported on TiO2 combined with a Cu-ZnO(Al) catalyst in the direct synthesis of dimethyl ether (DME) from syngas has been investigated. In this work, different types of TiO2 were used as a support to study the effect of changes in the structure of the TiO2 support on the acidity and dispersion of HPW. Various TiO2 supports with different structural and surface characteristics have been studied and the results indicate that: (i) the crystallinity and crystallite size of the primary particles of the HPW units depend on the TiO2 support; (ii) the pore size distribution of the TiO2 support affects the surface segregation of the heteropolyacids; and (iii) changes in the supported HPW acid catalysts do not significantly alter the crystal structure of the CuO and ZnO phases after contact with CZA in bifunctional catalysts. The activity results indicate that the variation in the intrinsic activity of the Cu-ZnOx centers in the bifunctional catalysts for direct DME synthesis is minimal due to the limited alteration of the crystal structure of the centers.

Interfacial engineering and vacancy design of quasi-2D NiCoAl-LDH/Kaolin hybrid for activating peroxymonosulfate to boost degradation of antibiotics

Oxygen vacancies are prevalent in metal compounds and play a significant role in the activation of peroxomonosulfate (PMS) to mitigate water pollution. However, how to easily construct these oxygen vacancies and elucidate the mechanism of PMS activation by oxygen vacancies are still pending research and solution. This study presents the synthesis of a NiCoAl-LDH/Kaolin (NiCoAl-LDH/Kao) hybrid catalyst with quasi-2D layer structures morphology and abundant oxygen vacancies (OVs) for activating peroxymonosulfate (PMS). We proposed an intriguing phase transformation from NiCo-carbonate hydroxide (CH) to NiCoAl-layered double hydroxide (LDH), and elucidated the morphological evolution mechanism from nanorod to nanosheet structures through alkaline etching. The NiCoAl-LDH/Kao-PMS system exhibited excellent rapid kinetics and removal efficiency of norfloxacin (NOR), degrading 92.0 % of NOR within 10 min and achieving a final degradation rate of 97.2 %, along with remarkable reusability performance of the NiCoAl-LDH/Kao catalyst. Furthermore, reactive oxygen species including sulfate radical (SO4−), hydroxyl radical (OH), superoxide anion (O2−) and singlet oxygen (1O2) were found to be involved in the degradation process of NOR, and the degree of activity of the active groups from strong to weak is 1O2, SO4−, O2− and OH. The activation mechanism and conceivable degradation pathways of NOR were experimentally studied and proposed, and the toxicity of degradation intermediates was evaluated. The facile preparation method for NiCoAl-LDH/Kao nanocomposite holds potential for large-scale manufacturing in organic pollutant remediation, while also providing new insights on the indispensable role of OVs in heterogeneous catalysis.

Conversion of syngas into lower olefins over a hybrid catalyst system

Conversion of syngas into lower olefins over a hybrid catalyst system

Halloysite-kojic acid conjugate: A sustainable material for the photocatalytic CO2 reduction and fixation for cyclic carbonates production

This study introduces a straightforward synthesis method for producing a hybrid material composed of halloysite and kojic acid, which catalyzes carbon dioxide (CO2) conversion processes. Kojic acid, derived from malted rice fermentation, exhibits inherent chelating properties that facilitate the introduction of copper ions onto the material’s surface. Copper ions, an economically viable alternative to noble metals, catalyze CO2 conversion reactions effectively. The hybrid catalyst was evaluated for two distinct CO2 conversion pathways: photocatalytic methane production under simulated sunlight and CO2 fixation into cyclic carbonates via epoxide reactions. The hybrid material demonstrates remarkable catalytic activity under mild conditions, achieving high conversion efficiencies at 45 °C for methane production and 70 °C for carbonate fixation at atmospheric pressure. Conversion of 31 % and 89 % were achieved for the photocatalytic CO2 reduction and the carbonate fixation, respectively. FT-IR spectra confirmed the functionalization of the material. Additionally, its organic/inorganic hybrid nature is complemented by excellent thermal stability, as studied by TGA. It enables repeated utilization, maintaining a 25 % catalytic activity for methane production and 70 % for carbonate fixation after the fourth reuse. This research highlights the potential of using naturally derived materials for sustainable CO2 mitigation.

Catalytic coupling of CO2 and epoxides with metal substituted Keggin based Hybrid Materials

Three hybrid catalytic materials are synthesised using transition metal (CoII, NiII, CuII) substituted lacunary Keggin polyoxometalates and tetrabutylammonium cations (TBA-TMSPOMs) and used for atom-economic cycloaddition of carbon dioxide to various epoxides producing cyclic carbonates under ambient conditions. These hybrid materials have been characterised by powder XRD, TGA, SEM, TEM, FTIR and 31P NMR. A rapid and effective method towards quantitative conversion of aliphatic, cyclic, and aromatic epoxides to their respective cyclic carbonates under solvent-free conditions is described. The percentage conversion of various epoxides into their respective cyclic carbonates is confirmed by 1H NMR and gas chromatography. Of all the cyclcoaddition reactions studied, the epichlorohydrin shows nearly 100% selectivity with turnover frequency of 244 h−1. Among the three hybrid catalysts, ∼0.12 mol% of TBA-PWCo is adequate to achieve highest catalytic efficiency with over 95% conversion in 4 h at RT. This catalyst is recyclable and reusable up to five cycles without significant loss in activity.

Selective production of high-value fuel via catalytic upgrading of bio-oil over nitrogen-doped carbon-alumina hybrid supported cobalt catalysts

Bio-oil derived from biomass fast pyrolysis can be upgraded to gasoline and diesel alternatives by catalytic hydrodeoxygenation (HDO). Here, the novel nitrogen-doped carbon–alumina hybrid supported cobalt (Co/NCAn, n = 1, 2.5, 5) catalyst is established by a coagulation bath technique. The optimized Co/NCA2.5 catalyst presented 100 % conversion of guaiacol, high selectivity to cyclohexane (93.6 %), and extremely high deoxygenation degree (97.3 %), respectively. Therein, the formation of cyclohexanol was facilitated by stronger binding energy and greater charge transfer between Co and NC which was unraveled by density functional theory calculations. In addition, the appropriate amount of Lewis acid sites enhanced the cleavage of the C–O bond in cyclohexanol, finally resulting in a remarkable selectivity for cyclohexane. Finally, the Co/NCA2.5 catalyst also exhibited excellent selectivity (93.1 %) for high heating value hydrocarbon fuel in crude bio-oil HDO. This work provides a theoretical basis on N dopants collaborating alumina hybrid catalysts for efficient HDO reaction.

Molecular Terpyridine-Lanthanide Complexes Modified Carbon Nitride for Enhanced Photocatalytic CO2 Reduction.

Molecule/semiconductor hybrid catalysts, which combine molecular metal complexes with semiconductors, have shown outstanding performances in photocatalytic CO2 reduction. In this work, we report two hybrid catalysts for the selective photoreduction of CO2 to CO. One is composed of carbon nitride and a terpyridine-Lu complex (denoted as LutpyCN), and the other is composed of carbon nitride and a terpyridine-Ce complex (denoted as CetpyCN). Compared with pristine carbon nitride, the hybrid catalysts LutpyCN and CetpyCN display a noteworthy increase in CO generation, boosting the yield by approximately 176 times and 106 times, respectively. Mechanistic studies demonstrate that such significant enhancement in photocatalysis is primarily due to more efficient separation of photogenerated carriers for hybrid catalysts after modifying CN with molecular terpyridine-lanthanide species.