北海道大学 · Materials Science
Takashi Toyao 교수의 연구실은 광촉매 및 촉매를 활용한 탄소 포집 및 활용 기술, 특히 이산화탄소를 메탄올로의 효율적 수소화와 수소 생산에 중점을 두고 있습니다. 다양한 금속-유기 프레임워크(MOF) 및 나노촉매를 설계하여, 가시광선 조건 하에서도 높은 활성도와 선택성을 확보하는 연구를 진행하고 있습니다. 특히, 플라티넘, 루테늄, 레늄, Copper 등 다양한 촉매 종류를 MOF 기반 구조에 통합함으로써, 에너지 전환과 환경 친화적 화학공정 실현에 기여하고 있습니다.
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Efficient hydrogen production and photocatalytic reduction of nitrobenzene were achieved by using a Pt-deposited amino-functionalised Ti(IV) metal–organic framework (Pt/Ti-MOF-NH2) under visible-light irradiation. XRD and N2 adsorption measurements revealed that crystalline microporous structures were formed and maintained even after the Pt deposition. The photocatalytic activity for the visible-light-promoted hydrogen production was improved through the optimization of the deposition amount of
A Ru complex-incorporated Ti-based MOF (Ti-MOF-Ru(tpy)2) has been synthesised by using a bis(4'-(4-carboxyphenyl)-terpyridine)Ru(ii) complex (Ru(tpy)2) as an organic linker. Ti-MOF-Ru(tpy)2 promotes photocatalytic hydrogen production from water containing a sacrificial electron donor under visible-light irradiation up to 620 nm.
Hydrogenation of carbon dioxide (CO2) to methanol (MeOH) is an effective strategy for CO2 utilization. Because of a low equilibrium conversion of CO2 to MeOH at high temperature, development of efficient catalytic CO2 hydrogenation processes that operate under low reaction temperature is of extreme importance. Herein, we report that TiO2-supported Re (Re(1)/TiO2; Re = 1 wt %) promotes the selective hydrogenation of CO2 to MeOH (total TON based on Re = 44, MeOH selectivity = 82%) under mild condi
A Zr-based metal-organic framework with tetrakis(carboxyphenyl)porphyrin groups (Zr-MOF-TCPP: MOF-525) has been utilized as a photoredox catalyst to promote oxidative hydroxylation of arylboronic acids under green LED light irradiation. Zr-MOF-TCPP displays a superior catalytic activity for this process over the corresponding homogeneous catalyst (H4TCPP).
A catalytically competent Cu species has been immobilized within the framework of a Zr-based metal–organic framework with bipyridine units, Zr-MOF-bpy, by a simple postsynthetic modification method from CuBr2 (Zr-MOF-bpy-CuBr2) and used for the selective oxidation of cyclooctene to cyclooctene oxide. Zr-MOF-bpy was synthesized by a simple solvothermal method and was shown to have a UiO-type structure. Diffuse reflectance UV–vis and XAFS measurements have revealed that the immobilized Cu species
Herein, we report a heterogeneous TiO<sub>2</sub> -supported Re catalyst (Re/TiO<sub>2</sub> ) that promotes various selective hydrogenation reactions, which includes the hydrogenation of esters to alcohols, the hydrogenation of amides to amines, and the N-methylation of amines, by using H<sub>2</sub> and CO<sub>2</sub> . Initially, Re/TiO<sub>2</sub> was evaluated in the context of the selective hydrogenation of 3-phenylpropionic acid methyl ester to afford 3-phenylpropanol (pH2 =5 MPa, T=180 °
Efficient conversion of CO2 into useful chemicals, exemplified by the development of methods for low-temperature hydrogenation of CO2 to form methanol (CH3OH), is a highly attractive research target. Herein, we report that Pt nanoparticles, loaded on MoOx/TiO2 as a support (Pt(3)/MoOx(30)/TiO2; Pt 3 wt %, MoO3 30 wt %), promote selective hydrogenation of CO2 to produce CH3OH in 73% yield under mild conditions (T = 150 °C; t = 48 h; pCO2 = 1 MPa; pH2 = 5 MPa). It is significant that the observed
The Front Cover shows a C−N bond cleavage reaction catalyzed by CeO2. In their Full Paper, T. Toyao et al. demonstrate that CeO2 promotes catalytic alcoholysis reactions of tertiary amides through C−N bond cleavage to form esters. Unlike typical reactions that use homogeneous catalytic systems and require NHC complexes, the new process is operationally convenient and does not require additives. In addition, the catalyst is recyclable and the process has a wide substrate scope. Both experimental
The amino-functionalised metal–organic framework, MIL-101(Al)-NH2, has been synthesized by using a solvothermal method and employed as a bifunctional acid–base catalyst for a one-pot, sequential deacetalization–Knoevenagel condensation reaction. In preliminary studies, the abilities of MIL-101(Al)-NH2 to serve as an acid and base catalyst were explored separately by two typical acid- and base-catalysed reaction, that is, deacetalization of benzaldehyde dimethylacetal and Knoevenagel condensation
A novel one-pot reaction system is developed by utilizing a bifunctional metal–organic framework photocatalyst (Zr-MOF-NH2). Zr-MOF-NH2 promotes sequential photocatalytic oxidation and Knoevenagel condensation reaction to produce benzylidenemalononitrile from benzyl alcohol and malononitrile under UV-light irradiation.
TiO<sub>2</sub> -supported Re, Re/TiO<sub>2</sub> , was found to promote selective hydrogenation of carboxylic acids having aromatic and aliphatic moieties to the corresponding alcohols. Re/TiO<sub>2</sub> showed superior results compared to other transition-metal-loaded TiO<sub>2</sub> and supported Re catalysts for selective hydrogenation of 3-phenylpropionic acid. 3-phenylpropanol was produced in 97 % yield under mild conditions (5 MPa H<sub>2</sub> at 140 °C). Contrary to typical heterogeneo
A Cu-based metal–organic framework (HKUST-1) was synthesized from insoluble precursors and positioned using sol–gel based coatings.
Various N-doped nanoporous carbons containing metal species were prepared by direct thermal conversion of zeolitic imidazolate frameworks (ZIFs; ZIF-7, -8, -9, and -67) at different temperatures (600, 800, and 1000 °C). These materials were utilized as bifunctional acid-base catalysts to promote the reaction of CO2 with epoxides to form cyclic carbonates under 0.6 MPa of CO2 at 80 °C. The catalyst generated by thermal conversion of ZIF-9 at 600 °C (C600-ZIF-9) was found to exhibit a higher catal
Pt/MoO<sub>x</sub>/TiO<sub>2</sub> shows excellent catalytic performance for the reverse water-gas shift reaction at 250 °C <italic>via</italic> reverse Mars–van Krevelen mechanism.