Catalytic Conversion of Biomass-Derived Levulinic Acid to γ-Valerolactone over Amphoteric Zirconium Hydroxide

Rong Zhao; Saravanan Kasipandi; Chae Ho Shin; Jong Wook Bae

doi:10.1021/acscatal.3c02860

Catalytic Conversion of Biomass-Derived Levulinic Acid to γ-Valerolactone over Amphoteric Zirconium Hydroxide

Rong Zhao
, Saravanan Kasipandi
, Chae Ho Shin
, Jong Wook Bae^*

^*Corresponding author for this work

BA5205 Chemical and polymer synthesis

Research output: Contribution to journal › Article › Scientific › peer-review

36 Citations (Scopus)

Abstract

A series of acid-base amphoteric amorphous Zr(OH)₄ catalysts, synthesized with different amounts of leached SiO₂, were investigated for catalytic transfer hydrogenation of liquid-phase levulinic acid (LA) to produce γ-valerolactone (GVL) with isopropanol as a hydrogen-donor solvent. The prepared Zr(OH)₄ at pH of ∼10 under a reflux condition of water caused an inevitable dissolution of silicon species from glassware, which eventually altered the surface acid-basic properties of the amorphous Zr(OH)₄. The number of Lewis and total acidic as well as medium-strength basic sites, prepared by simply changing the aging days of Zr(OH)₄, was mainly responsible for an enhanced LA conversion of 91.5% and GVL selectivity of 77.6% with an apparent activation energy of ∼33.9 kJ/mol over Zr(OH)₄ aged for 7 days [ZrOH (7)]. In addition, catalytic and thermal stabilities of ZrOH (7) were found with a stable LA conversion with smaller coke depositions, which were attributed to the stable preservation of the active sites caused by a proper amount of thermally stable Zr-O-Si phase formation.

Original language	English
Pages (from-to)	12711-12722
Journal	ACS Catalysis
Volume	13
Issue number	19
DOIs	https://doi.org/10.1021/acscatal.3c02860
Publication status	Published - 6 Oct 2023
MoE publication type	A1 Journal article-refereed

Funding

The authors would like to sincerely acknowledge the financial support from the National Research Foundation of Korea (NRF) grant funded by the Korea government (project #: NRF-2021R1A4A1024129 and NRF-2018M3D3A1A01018009). This work was also supported by the Korea Institute for Advancement of Technology (KIAT) and the Ministry of Trade, Industry & Energy (MOTIE) of the Republic of Korea (no. P0017363).

Keywords

acidic and basic sites
amphoteric zirconium hydroxide (Zr(OH))
catalytic transfer hydrogenation (CTH)
levulinic acid
γ-valerolactone

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10.1021/acscatal.3c02860

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@article{316c7f94d70c42f0aac2c4a8bf555b3f,

title = "Catalytic Conversion of Biomass-Derived Levulinic Acid to γ-Valerolactone over Amphoteric Zirconium Hydroxide",

abstract = "A series of acid-base amphoteric amorphous Zr(OH)4 catalysts, synthesized with different amounts of leached SiO2, were investigated for catalytic transfer hydrogenation of liquid-phase levulinic acid (LA) to produce γ-valerolactone (GVL) with isopropanol as a hydrogen-donor solvent. The prepared Zr(OH)4 at pH of ∼10 under a reflux condition of water caused an inevitable dissolution of silicon species from glassware, which eventually altered the surface acid-basic properties of the amorphous Zr(OH)4. The number of Lewis and total acidic as well as medium-strength basic sites, prepared by simply changing the aging days of Zr(OH)4, was mainly responsible for an enhanced LA conversion of 91.5\% and GVL selectivity of 77.6\% with an apparent activation energy of ∼33.9 kJ/mol over Zr(OH)4 aged for 7 days [ZrOH (7)]. In addition, catalytic and thermal stabilities of ZrOH (7) were found with a stable LA conversion with smaller coke depositions, which were attributed to the stable preservation of the active sites caused by a proper amount of thermally stable Zr-O-Si phase formation.",

keywords = "acidic and basic sites, amphoteric zirconium hydroxide (Zr(OH)), catalytic transfer hydrogenation (CTH), levulinic acid, γ-valerolactone",

author = "Rong Zhao and Saravanan Kasipandi and Shin, \{Chae Ho\} and Bae, \{Jong Wook\}",

note = "Publisher Copyright: {\textcopyright} 2023 American Chemical Society.",

year = "2023",

month = oct,

day = "6",

doi = "10.1021/acscatal.3c02860",

language = "English",

volume = "13",

pages = "12711--12722",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society ACS",

number = "19",

}

TY - JOUR

T1 - Catalytic Conversion of Biomass-Derived Levulinic Acid to γ-Valerolactone over Amphoteric Zirconium Hydroxide

AU - Zhao, Rong

AU - Kasipandi, Saravanan

AU - Shin, Chae Ho

AU - Bae, Jong Wook

PY - 2023/10/6

Y1 - 2023/10/6

N2 - A series of acid-base amphoteric amorphous Zr(OH)4 catalysts, synthesized with different amounts of leached SiO2, were investigated for catalytic transfer hydrogenation of liquid-phase levulinic acid (LA) to produce γ-valerolactone (GVL) with isopropanol as a hydrogen-donor solvent. The prepared Zr(OH)4 at pH of ∼10 under a reflux condition of water caused an inevitable dissolution of silicon species from glassware, which eventually altered the surface acid-basic properties of the amorphous Zr(OH)4. The number of Lewis and total acidic as well as medium-strength basic sites, prepared by simply changing the aging days of Zr(OH)4, was mainly responsible for an enhanced LA conversion of 91.5% and GVL selectivity of 77.6% with an apparent activation energy of ∼33.9 kJ/mol over Zr(OH)4 aged for 7 days [ZrOH (7)]. In addition, catalytic and thermal stabilities of ZrOH (7) were found with a stable LA conversion with smaller coke depositions, which were attributed to the stable preservation of the active sites caused by a proper amount of thermally stable Zr-O-Si phase formation.

AB - A series of acid-base amphoteric amorphous Zr(OH)4 catalysts, synthesized with different amounts of leached SiO2, were investigated for catalytic transfer hydrogenation of liquid-phase levulinic acid (LA) to produce γ-valerolactone (GVL) with isopropanol as a hydrogen-donor solvent. The prepared Zr(OH)4 at pH of ∼10 under a reflux condition of water caused an inevitable dissolution of silicon species from glassware, which eventually altered the surface acid-basic properties of the amorphous Zr(OH)4. The number of Lewis and total acidic as well as medium-strength basic sites, prepared by simply changing the aging days of Zr(OH)4, was mainly responsible for an enhanced LA conversion of 91.5% and GVL selectivity of 77.6% with an apparent activation energy of ∼33.9 kJ/mol over Zr(OH)4 aged for 7 days [ZrOH (7)]. In addition, catalytic and thermal stabilities of ZrOH (7) were found with a stable LA conversion with smaller coke depositions, which were attributed to the stable preservation of the active sites caused by a proper amount of thermally stable Zr-O-Si phase formation.

KW - acidic and basic sites

KW - amphoteric zirconium hydroxide (Zr(OH))

KW - catalytic transfer hydrogenation (CTH)

KW - levulinic acid

KW - γ-valerolactone

UR - https://www.scopus.com/pages/publications/85174723848

U2 - 10.1021/acscatal.3c02860

DO - 10.1021/acscatal.3c02860

M3 - Article

AN - SCOPUS:85174723848

SN - 2155-5435

VL - 13

SP - 12711

EP - 12722

JO - ACS Catalysis

JF - ACS Catalysis

IS - 19

ER -

Catalytic Conversion of Biomass-Derived Levulinic Acid to γ-Valerolactone over Amphoteric Zirconium Hydroxide

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