Catalytic Transfer Hydrogenation Reaction Research Articles

The effect of modulator in the synthesis of UiO-66(Zr) and UiO-67(Zr) and their performances in catalytic transfer hydrogenation reaction of α-angelica lactone to γ-valerolactone

The effect of modulator in the synthesis of UiO-66(Zr) and UiO-67(Zr) and their performances in catalytic transfer hydrogenation reaction of α-angelica lactone to γ-valerolactone

A Novel Mesoporous SBA‐15 Supported Bifunctional Heterogeneous Catalyst for Base‐Free Transfer Hydrogenation Reaction of Ketones

ABSTRACTAmong the problems encountered in the catalytic transfer hydrogenation reactions of ketones, the base sensitivity of ketones and the corrosive effects of the bases used in the reaction have an important place especially in industrial terms. Although there are various approaches to overcome this problem, solutions based on the intrinsic properties of the catalyst used seem more suitable. Within the scope of this study, a novel heterogeneous catalyst was prepared for the transfer hydrogenation reaction of ketones, which can operate in base‐free environment. To prepare the heterogeneous catalyst, 1,2‐diphenylethane‐1,2‐diamine was first tosylated and then the silyl derivative was synthesized and grafted onto mesoporous silica SBA‐15. Characterizations of the obtained heterogeneous catalyst and SBA‐15 were carried out by X‐ray diffractometer (XRD), N2 sorption, thermogravimetric analysis (TGA), scanning electron microscope (SEM), energy dispersive X‐ray analysis, and Fourier transform infrared (FT‐IR) analysis. The results obtained showed that the functionalized 1,2‐diphenylethane‐1,2‐diamine compound was successfully immobilized into the SBA‐15 structure. Determination of the catalytic activity of the heterogeneous catalyst was carried out in transfer hydrogenation reactions of various aromatic ketones. After determining the optimum reaction conditions with acetophenone, a conversion rate of (70%) was observed in the acetophenone to 1‐phenylethanol reaction that took place without a base. Under same conditions a higher conversion rate of (73%) was observed in the 4′‐chloroacetophenone to 1‐(4‐chlorophenyl)ethanol reaction. In the reactions performed to determine recyclability, after a 70% conversion rate, 61% and 65% conversion rates, respectively, were observed in the reaction from acetophenone to 1‐phenylethanol under the same conditions.

Single nickel atoms anchored on porous N-doped nanocarbon with dual reaction sites for highly-efficient transfer hydrogenation of furfural to furfuryl alcohol

The non-precious metal single-atom catalysts (SACs) supported on carbon materials for the catalytic transfer hydrogenation (CTH) of α,β-unsaturated aldehydes (UAL) still suffer from the problems of harsh reaction conditions and low activity. In this work, nickel SACs anchored on porous N-doped nanocarbon (Ni1/NC900) with dual reaction sites were synthesized using the high internal-phase emulsion (HIPE) template method combined with impregnation. The Ni1/NC900 catalyst exhibited remarkable catalytic activity for the CTH of furfural (FF) to furfuryl alcohol (FFA), achieving >99.0 % conversion and selectivity at 100 °C for 60 min, with a turnover frequency (TOF) of 2908.1 h−1, surpassing other reported nickel-based catalysts by 1–3 orders of magnitude. The excellent catalytic performance of Ni1/NC900 was attributed to the high mass transfer efficiency (HMTE) of the support and the dual reaction sites of Ni–N4 and pyridinic N, where Ni–N4 as Lewis acidic site for adsorption of FF and isopropanol (i-PrOH), while the adjacent pyridinic N as Lewis basic site for the deprotonation of i-PrOH. The isotope labeling experiments revealed that the hydrogenation of FF was accomplished by proton transfer with i-PrOH, in agreement with the intermolecular hydride transfer mechanism. Furthermore, Ni1/NC900 demonstrated excellent stability and well general applicability, demonstrating its potential for industrial applications. This work provides a reference for the application of carbon-based non-precious metal SACs in the CTH reaction of UAL.

(Invited) Thermal and Plasmon-Mediated Catalytic Transfer Hydrogenation Reactions on Nanostructured Metal Surfaces

Catalytic hydrogenation reactions play crucial roles in fine chemical production and pharmaceutical synthesis. Compared to direct hydrogenation of organic compounds with pressurized hydrogen gas, catalytic transfer hydrogenation reactions using inexpensive and readily accessible small molecules as hydrogen-donors has been considered as a more versatile, scalable, and sustainable pathway toward enhanced chemoselectivity under mild reaction conditions. Noble metal nanoparticles, especially those within the sub-5 nm size regime, can efficiently catalyze the dehydrogenation of a series of hydrogen-storing molecules, such as ammonia borane, hydrazine, formaldehyde, formic acid, and isopropanol, to produce surface-adsorbed hydrogen species that actively hydrogenate a variety of organic substrate molecules. The transfer hydrogenation/hydrogenolysis reactions are mechanistically complex, and may occur selectively along multiple distinct pathways, exhibiting kinetic features signifying the Langmuir–Hinshelwood, Eley–Rideal, autocatalysis, and reversible reaction mechanisms, respectively, depending on the compositions of the metal catalysts and the chemical nature of the hydrogen donors. In this talk, I will share with the audience some new insights concerning the detailed mechanisms of transfer hydrogenation reactions over metal nanocatalyst surfaces. We employ surface-enhanced Raman scattering (SERS) as an in situ fingerprinting spectroscopic tool to precisely resolve the detailed structural evolution of molecular adsorbates during catalytic reactions, based upon which the key intermediates along different reaction pathways are unambiguously identified. The results of deliberately designed in situ SERS measurements show that the chemoselective transfer hydrogenation of nitrophenyl isocyanide by ammonia borane may proceed on noble metal nanocatalyst surfaces selectively through either a unimolecular or a bimolecular pathway, depending on how the nitrophenyl isocyanide adsorbates interact with the metal nanoparticle surfaces. The experimental observations are corroborated by density functional theory calculations, which shed light on the underlying relationships between catalyst-adsorbate interactions and reaction pathway selection. We have further demonstrated that the photoexcited plasmonic hot carriers in the metal nanoparticles can be effectively harnessed to fine-regulate the activation energy barriers associated with the rate-limiting steps for the transfer hydrogenation of nitrophenyl isocyanide on Pd nanocatalyst surfaces when ammonium formate serves as the hydrogen donor. Our results clearly demonstrate the feasibility of using plasmonic hot carriers to kinetically modulate catalytic molecule-transforming processes.

Iridium(III) complexes with cyclometalated imidazolylidene ligands: sp2 phenyl C[sbnd]H activation vs sp2 benzyl C[sbnd]H activation and catalytic transfer hydrogenation reactions

Cyclometalated N-heterocyclic carbene (NHC) complexes possess fascinating electronic and catalytic properties. A series of cyclometalated iridium(III) complexes have been synthesized from the corresponding imidazolium salts via the aryl sp2 CH bond activation at the N1-phenyl/N3-benzyl wingtips of the imidazolylidene moiety. The electronic tuning towards the competitive formation of cyclometalated complexes (sp2 phenyl CH activation vs sp2 benzyl CH activation) has been discussed. These complexes have been utilized for the transfer hydrogenation (TH) reaction of 4-bromobenzaldehyde and 4-bromoacetophenone. These complexes showed excellent yields of the aryl-alcohols from 4-bromobenzaldehyde or 4-bromoacetophenone.

Acid-base synergistic effect towards catalytic transfer hydrogenation reactions

Catalytic transfer hydrogenation (CTH) of aldehydes/ketones by using alcohols as hydrogen donors is an attractive and environmentally friendly hydrogenation technology, which has evoked widespread attention in synthesis of fine chemicals from biomass resources. In this work, a Co-Al mixed metal oxide catalyst (Co1Al2-MMO-200) was obtained through structural topological transformation process of layered double hydroxides, which was used in the CTH reaction of furfural with isopropanol. Notably, the reaction rate achieves 0.023 mol g−1 h−1, which is preponderate to acid-base catalysts earlier reported. The joint research based on CO2-TPD, NH3-TPD and poisoning experiment substantiates that the synergy effect of acid-base sites plays an essential role in this catalytic system. Isotopic labelling MS, in-situ FT-IR and DFT studies further verify that the CTH reaction of furfural occurs via the Meerwein-Ponndorf-Verley (MPV) route, in which the basic site promotes the deprotonation of isopropanol whilst the acid site facilitates the formation of a six-membered ring transition state. This work demonstrates an acid-base synergetic catalysis for the CTH reaction by revealing the structure-property correlation and exploring reaction route, which is instructive for designing high-performance heterogenous catalysts.

Zn Single-Atom Catalysts Enable the Catalytic Transfer Hydrogenation of α,β-Unsaturated Aldehydes.

Highly active nonprecious-metal single-atom catalysts (SACs) toward catalytic transfer hydrogenation (CTH) of α,β-unsaturated aldehydes are of great significance but still are deficient. Herein, we report that Zn-N-C SACs containing Zn-N3 moieties can catalyze the conversion of cinnamaldehyde to cinnamyl alcohol with a conversion of 95.5% and selectivity of 95.4% under a mild temperature and atmospheric pressure, which is the first case of Zn-species-based heterogeneous catalysts for the CTH reaction. Isotopic labeling, in situ FT-IR spectroscopy, and DFT calculations indicate that reactants, coabsorbed at the Zn sites, proceed CTH via a "Meerwein-Ponndorf-Verley" mechanism. DFT calculations also reveal that the high activity over Zn-N3 moieties stems from the suitable adsorption energy and favorable reaction energy of the rate-determining step at the Zn active sites. Our findings demonstrate that Zn-N-C SACs hold extraordinary activity toward CTH reactions and thus provide a promising approach to explore the advanced SACs for high-value-added chemicals.

Synthesis of the Pentasaccharide of the K14 Capsular Polysaccharide of Antibiotic Resistant ST25 Acinetobacter baumannii isolate, D46 and O‐Polysaccharide of Acinetobacter baumannii O11

AbstractSynthesis of the pentasaccharide corresponding to the K14 capsular polysaccharide from ST25 Acinetobacter baumannii isolate, D46 and O‐polysaccharide of Acinetobacter baumannii O11 has been achieved in very good yield using a convergent stereoselective [3+2] block glycosylation strategy. The synthetic scheme includes several regio‐ and stereose lective glycosylations as well as orthogonal glycosylation with high yield. Thioglycosides have been used as glycosyl donors using a combination of copper(II) bromide and tetra‐n‐butylammonium bromide (TBAB) as thiophilic activator for 1,2‐cis glycosylation and a combination of N‐iodosuccinimide (NIS) and trimethylsilyl trifluoromethanesulfonate (TMSOTf) as thiophilic activator for 1,2‐trans glycosylation. Glycosyl trichloroacetimidate derivative was used as glycosyl donor using perchloric acid supported on silica (HClO4–SiO2) as activator. A catalytic transfer hydrogenation reaction has been carried out for the removal of benzyloxy and benzylidene functional groups using triethylsilane as hydrogen source.

Stabilization of unique Zr>4+ species in NiFe2O4 nanocrystals for unprecedented catalytic transfer hydrogenation reaction

Stabilization of transition metal species (like Zr>4+) with increasingly positive charge density at oxide surfaces is highly important for intrinsically improving catalytic performance for many uses like catalytic transfer hydrogenation (CTH) reaction, which however remains inaccessible. Here, we showcase a water-quenching strategy that stably achieves Zr>4+ species at surfaces of prototype spinel oxide NiFe2O4. Systematic investigation unveils that these Zr>4+species were precisely incorporated into surface octahedral Ni sites of NiFe2O4. The local electronic structure was thus regulated. As a consequence, there simultaneously appear electron depletion (Zr>4+) and accumulation (O2-) at the resulted sites, which play the distinct roles as Lewis acid-base sites in (i) facilitating O-H bond dissociation and CO bond activation, (ii) enhancing the interaction and bonding with substrate molecules, and (iii) reducing the energy barrier for hydrogen transfer process. The resulting catalysts exhibit superior catalytic performance and stability in the CTH reaction of biomass-derived carbonyls and representative aldehydes/ketones, especially the reduction of furfural to furfuryl alcohol with a yield of 90.7% under 120 ℃ for 3 h. This work provides new insights into optimizing catalytic activity in metal oxides by stabilizing transition metal species with unexpectedly positive charge density.

Catalytic aqueous hydrodeoxygenation of palmitic acid with in-situ hydrogen donor

Algal bio-oil obtained from hydrothermal liquefaction of algae contains a large amount of water and long-chain fatty acids. High acidity and corrosiveness seriously restrict the application of algal bio-oil. The aqueous-phase catalytic upgrading was a promising approach to solve this problem, and the hydrogen donor was one of the most important parameters to the conversion of the algal bio-oil and the quality of the products. Catalytic transfer hydrogenation (CTH) reaction was an efficient, economical and green method for hydrogenation reaction, which can directly transfer hydrogen from the hydrogen donor to the reaction substrate. In this work, the CTH reaction of algal bio-oil model compound palmitic acid was investigated to deal with the problem of high oxygen content in the algal bio-oil. Several common hydrogen donors, included methanol, ethanol, formic acid, and isopropanol, as well as different reaction conditions were experimented to study the CTH process of palmitic acid. The results showed that, with the reaction conditions of 350 °C and 10 h, formic acid achieved the best oxygen removal, carbon retention and energy efficiency, the C16 selectivity reached the highest at 33.3 % as the formic acid addition ratio was 1:2, and the C15 selectivity reached the highest at 48.3 % as the formic acid addition ratio was 1:3. In general, the best ratio of formic acid added was 1:3, which showed the highest yield of C15 and above alkanes of 79.6 %. This result indicates that the catalytic transfer hydrogenation reaction of formic acid has practical value in improving the combustion performance of algal bio-oil.

Rigorous design, techno-economic and environmental analysis of two catalytic transfer hydrogenation (CTH) processes to produce bio-based 2-methylfuran (2-MF)

The catalytic transfer hydrogenation (CTH) reaction has emerged as a safer method for converting biomass derivatives into value-added chemicals. This study aims to comprehensively evaluate two processes for converting furfural into 2-methylfuran (2-MF) using either methanol (or MeOH, Scheme 1) or isopropyl alcohol (or IPA, Scheme 2) as hydrogen carriers. Both processes were rigorously simulated using Aspen Plus. The reaction performance was modeled using kinetic models developed from literature data. In addition, appropriate strategies are first established for separating the reactor effluents of both processes, which contain multiple azeotropes, based on the thermodynamic parameters estimated through COSMO-based calculations. From the techno-economic analysis, the minimum required selling price (MRSP) of 2-MF is 5.15 USD/kg when produced with Scheme 1, and 3.63 USD/kg when produced with Scheme 2. The MRSP in Scheme 1 becomes 4.50 USD/kg by considering the benefits of the side product, a formalin solution. Compared to various literature data, the MRSPs of these two process schemes are significantly lower than that obtained from direct hydrogenation (6.87 USD/kg). If the cost of the starting materials can be reduced by 25% or more, the MRSP becomes comparable to that obtained from an improved direct hydrogenation process (2.20–3.30 USD/kg). Furthermore, the CO2 emission analysis reveals that Scheme 2 has a lower rate of indirect CO2 emission rate (0.926 Ton-CO2/Ton-2-MF) compared to Scheme 1 (1.088 Ton-CO2/Ton-2-MF). With thorough assessment, we have concluded that the production of 2-MF through the CTH reaction in Scheme 2 is superior. This process shows promise in both economic and decarbonization aspects and could have industrial significance.

Ethanol as hydrogen donor: An efficient transfer hydrogenation of aldehydes, ketones, and nitroarenes with H-bonded Ru(II)-N-heterocyclic iminium complex

Isopropanol and formic acid are predominantly utilized as hydrogen sources in catalytic transfer hydrogenation reactions. However, the utilization of primary alcohols in such reactions has been sparsely documented, with only a limited number of reports available. In this article, we hereby present findings that underscore the prospective application of ecologically sustainable and economically viable ethanol, alongside a ruthenium(II) catalyst that exhibits remarkable resilience in the presence of moisture and oxygen. The air-stable Ru(II) complex (I) has been synthesized by non-covalently interacting anionic Ru(p-cymene)Cl3 and 1,3-diisopropyl-1H-perimidin-2(3H)-iminium (LH2+). The compound was subjected to experimental evaluation to conduct transfer hydrogenation reactions on aldehydes, ketones, and nitroarenes. The process entailed the utilization of ethanol, a hydrogen source that is both economically advantageous and ecologically benign. The hydrogen bond interaction existing between the Ru(p-cymene)Cl3 and LH2+ species plays a crucial in facilitating the exceptional catalytic efficiency exhibited by the Ru(II) complex (I). The reaction exhibits a wide range of substrate compatibility, enabling the hydrogenation of ketones, aldehydes, and nitroarenes. The results obtained from the control experiments have provided evidence for the formation of Ru − H species. A plausible mechanism has been hypothesized, relying on stoichiometric investigations.

Heterocyclic compounds: their potential application as antimicrobials of health importance and in the catalytic hydrogen transfer reaction

Heterocyclic compounds: their potential application as antimicrobials of health importance and in the catalytic hydrogen transfer reaction

Catalytic transfer hydrogenation of furfural via metal-organic framework-derived high entropy alloy catalysts at room pressure

Catalytic transfer hydrogenation (CTH), as an environmentally friendly selective hydrogenation method, has attracted great interest in the preparation of high value-added products from biomass-derived resources. Herein, the carbon-based high-entropy alloy (HEA) catalysts (PtCoNiCuZn@NC-X) were prepared via MOF derivatization, which exhibited good catalytic behavior for the CTH of furfural (FF) with isopropyl alcohol (IPA) as the hydrogen donor. The conversion of FF and selectivity of furfuryl alcohol (FOL) reached 100% at 100 °C without additional pressure via PtCoNiCuZn@NC-600 catalyst. Systematic characterization suggests that the abundance of strong acidic sites, high content of high-valent metals and appropriate alloy surface composition play a crucial role in determining the catalytic behavior. This work confirms the multi-sites synergistic catalysis of HEA, establishing structure-property correlations and revealing reaction pathways that can be extended to other CTH reactions in biomass upgrading processes.

Pt/CeCrO2−x: A multifunctional catalyst for tandem catalysis of lignocellulose hydro-liquefaction and Guerbet reaction

Catalytic transfer hydrogenation (CTH) of lignocellulose liquefaction using renewable ethanol presents a promising alternative to conventional hydrogenation techniques. However, the development of efficient and stable multifunctional catalysts remains a significant challenge. Herein, a Pt/Ce9Cr1O2−x catalyst was developed to facilitate the CTH reactions and achieve nearly complete utilization of lignocellulose. Isotope labeling experiments were conducted to elucidate the mechanism of CTH. The introduction of Cr3+ increased the density of surface oxygen vacancies, consequently enhancing the hydrodeoxygenation ability and metal anchoring. The solid solution structure promotes the electrons transfer from Cr atoms to Pt atoms, forming electron-rich Ptδ+ species that promote ethanol dehydrogenation and lignocellulose hydrodeoxygenation. Furthermore, Pt/Ce9Cr1O2−x catalyst provided optimal acid-base sites and hydroxyl groups, thereby improving ethanol upgrading efficiency and wettability.

Oxygenated groups enriched polyolefin-Zr(IV) complexes catalyzing low-temperature transfer hydrogenation of biomass-derived furfural with 2-propanol

Zr4+−O2− pairs in MOFs and macromolecule − Zr(IV) complexes have proved one of the ideal catalytic components for catalytic transfer hydrogenation of biomass-derived furfural. However, restricted by limited adjustability of Zr4+−O2− coordination environment and the complex design and creation of ligand defects, currently, there are only a few efficient low-temperature (<100 °C) catalytic systems. In this work, oxygenated groups enriched polyolefin − Zr(IV) complexes were prepared and fixed on/in mesoporous silica aerogel support. The complexes possessed a stable structure with CC bonds as the connecting skeleton of each oxygenated group, and the types and densities of oxygenated groups (COOH, SO3H, and OH) could be easily adjusted by using different monomers. In the catalytic transfer hydrogenation reaction of furfural and 2-propanol, the catalyst synthesized using dicarboxylic maleic acid as a monomer of polyolefin exhibited the best catalytic performance in low temperatures, the main product furfuryl alcohol with a high yield of 96.0 % and a high selectivity of 98.2 % was obtained at 85 °C for 8 h. In 6 cycles of reactions at 85 °C, the furfuryl alcohol yield decreased gradually from 96 % in the 1st cycle to 84.0 % in the 4th cycle and further restored to 90.9 % and 89.3 % in the 5th and 6th cycles, respectively, by refreshing the used catalyst with methanol washing, and there was almost no leaching of Zr4+ species in the reaction medium. The catalyst poisoning experiment with acidic and basic sites shielded by pyridine and boric acid, respectively, showed that the catalytic activity was more sensitive to the shielding of basic sites, and the isotope experiments revealed that two H of the product furfuryl alcohol are transferred from 2-propanol. Hereby, the oxygenated group-bearing polyolefin − Zr(IV) complexes with stable structure, variable functional groups and the corresponding various Zr4+−O2– coordination pairs, are ideal catalyst candidates for the selective transfer hydrogenation of furfural to furfuryl alcohol.

Reactivation of Ni-TiO2 catalysts in hydrogen flow and in supercritical 2-propanol-Comparative study by electron spin resonance in situ.

Highly dispersed Ni-TiO2 catalyst has been studied in the process of preparation and under catalytic transfer hydrogenation reaction conditions in supercritical 2-propanol (250°C, 70 bar) using electron spin resonance in situ. Electron spin resonance in situ has been used to study the process of the catalyst passivation and subsequent reduction of the oxide layer in the gas flow. Reduction of the NiO layer on the surface of passivated Ni nanoparticles has been detected in supercritical 2-propanol, which is in agreement with kinetic modeling data. It has been found that the reduction of the nickel oxide layer in supercritical 2-propanol occurs at a lower temperature compared with the reduction in hydrogen flow, according to in situ electron spin resonance study.

Sugars as Emerging Hydrogen Donors in the Synthesis of Alditol via Catalytic Transfer Hydrogenation

AbstractThe utilization of biomass‐derived sugars as the emerging hydrogen donor in catalytic transfer hydrogenation (CTH) reactions has received great attention in recent years. In this work, we proposed two CTH routes of alditol production in the aqueous solution, i. e. self‐disproportionation of sugar and cross CTH of different sugars. Both could realize the process of sugar towards alditol. Taking advantage of the differences in hydrogenation and dehydrogenation capabilities of different sugars, a high C4 alditol yield of 85.9 % was surprisingly obtained via cross CTH route using glucose as the hydrogen donor, which is much better than that obtained when using traditional hydrogen donor isopropanol. The CTH reactions using sugars as the hydrogen donor can not only reduce the utilization of fossil energy, but also provide a new pathway for the production of alditols.

Creation of surface frustrated Lewis pairs on high-entropy spinel nanocrystals that boosts catalytic transfer hydrogenation reaction

Creating frustrated Lewis pairs (FLPs) on stable high-entropy oxides (HEOs) is a new challenge, and also an uncultivated field in catalysis. Herein, holey layered HEO spinel nanocrystals with rich FLPs were synthesized via a temperature-driven topological transition. The FLPs on the surface of HEO spinel nanocrystals are created by oxygen vacancies (Lewis acid sites) and proximal surface hydroxyls or surface lattice oxygen (Lewis base sites). Rich FLPs furnish HEO nanocrystals a superior activity towards the catalytic transfer hydrogenation reaction of biomass-derived carbonyl compounds at mild conditions. The active regions in between FLPs provide a strong driving force for dissociating alcohols and activating carbonyl groups of substrates, as evidenced by the attenuated total reflectance-infrared spectroscopy (ATR-IR) analysis, which enhances the catalytic activity. This work develops a new kind of hydrogenation catalysts and provides a perspective for creating solid FLPs.

Construction of HfO2 nanoparticles with rich hydroxyl group for the efficient catalytic transfer hydrogenation of furfural

Although metal oxide has unique advantages in catalytic transfer hydrogenation (CTH) of furfural (FAL) into furfuryl alcohol (FOL), the excessive stability of the metal site and oxygen coordination leads to the inert Lewis acid site in the oxide, which affects the catalytic activity and limits its broader application. It is known that the hydroxyl group on the oxide surface can promote the adsorption of isopropanol in an alkoxide species by assisting its deprotonation, thereby activating the metal site and enhance the overall reaction activity. However, constructing metal oxide with rich hydroxyl groups is always challenging. This contribution prepared a series of HfO2 nanoparticles (NPs) with rich hydroxyl groups through hydrothermal methods. Systematic characterizations proved the presence of hydroxyl groups on the surface of HfO2 NPs, which promoted its adsorption capacity for isopropanol (hydrogen donor and reaction solvent) and substrate (FAL), thus accelerating the subsequent reaction for CTH of FAL into FOL. As a result, a 100% of FAL conversion with 95.2% of FOL yield was obtained at 160 °C in 4 h, which has significant advantages over commercial and other literature reported oxides. This finding provides a new idea for designing of efficient metal oxides for the CTH reaction by enhancing the hydroxyl group.