Correlation between acidity and catalytic performance of mesoporous zirconium oxophosphate in phenylglyoxal conversion

Haimei Xu, Zichun Wang, Zhichao Miao, Yuxiang Zhu, Aleksei Marianov, Lizhuo Wang, Patrice Castignolles, Marianne Gaborieau, Jun Huang, Yijiao Jiang

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The one-step conversion of α-keto aldehydes to α-hydroxy carboxylic acids and their derivatives using solid acids is of great appeal in biomass utilization. In this work, ordered mesoporous zirconium oxophosphate (ZrPO) catalysts with tunable acidity were prepared and their catalytic performance was evaluated using phenylglyoxal (PG) conversion to ethyl mandelate (EM). The roles of Lewis acid sites (LAS) and Brønsted acid sites (BAS) of ZrPO were investigated by kinetic studies of PG conversion combined with temperature-programmed desorption of ammonia (NH3-TPD) and solid-state NMR characterizations. It is found that the ratio of LAS to BAS on the ZrPO plays a dominant role in this reaction. ZrPO-0.75-500, with a LAS/BAS ratio of 2.1, was found to be the best catalyst. The reaction pathways, i.e., the direct isomerization of PG to EM by LAS and via the formation of an intermediate hemiacetal by BAS, are therefore proposed. Moreover, the effect of water on the catalytic activity was studied. A moderate amount of water induced either by catalyst pretreatment at the proper temperature or deliberately dosed on the ZrPO materials achieves a maximum catalytic activity. The highest catalytic activity, i.e., 82% of PG conversion and 92% of EM selectivity, was obtained on ZrPO-0.75-500 that was dosed by 15 μmol water per 50 mg of the catalyst. It is concluded that ZrPO with a suitable combination of LAS and BAS is required to efficiently and selectively catalyze the conversion of α-keto aldehydes to α-hydroxy carboxylic acid derivatives. It is feasible, from a practical point of view, to tune the density of LAS and BAS on the catalysts to achieve a better catalytic performance.

LanguageEnglish
Pages8931-8942
Number of pages12
JournalACS Sustainable Chemistry and Engineering
Volume7
Issue number9
DOIs
Publication statusPublished - 6 May 2019

Fingerprint

Phenylglyoxal
Lewis Acids
Zirconium
Acidity
acidity
Acids
acid
Catalysts
Catalyst activity
Temperature programmed desorption
Carboxylic Acids
catalyst
Aldehydes
Water
Derivatives
carboxylic acid
aldehyde
Carboxylic acids
Isomerization
Ammonia

Keywords

  • Brønsted acid sites
  • Lewis acid sites
  • Biomass utilization
  • Mesoporous zirconium oxophosphate
  • Solid-state NMR

Cite this

Xu, Haimei ; Wang, Zichun ; Miao, Zhichao ; Zhu, Yuxiang ; Marianov, Aleksei ; Wang, Lizhuo ; Castignolles, Patrice ; Gaborieau, Marianne ; Huang, Jun ; Jiang, Yijiao. / Correlation between acidity and catalytic performance of mesoporous zirconium oxophosphate in phenylglyoxal conversion. In: ACS Sustainable Chemistry and Engineering. 2019 ; Vol. 7, No. 9. pp. 8931-8942.
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abstract = "The one-step conversion of α-keto aldehydes to α-hydroxy carboxylic acids and their derivatives using solid acids is of great appeal in biomass utilization. In this work, ordered mesoporous zirconium oxophosphate (ZrPO) catalysts with tunable acidity were prepared and their catalytic performance was evaluated using phenylglyoxal (PG) conversion to ethyl mandelate (EM). The roles of Lewis acid sites (LAS) and Br{\o}nsted acid sites (BAS) of ZrPO were investigated by kinetic studies of PG conversion combined with temperature-programmed desorption of ammonia (NH3-TPD) and solid-state NMR characterizations. It is found that the ratio of LAS to BAS on the ZrPO plays a dominant role in this reaction. ZrPO-0.75-500, with a LAS/BAS ratio of 2.1, was found to be the best catalyst. The reaction pathways, i.e., the direct isomerization of PG to EM by LAS and via the formation of an intermediate hemiacetal by BAS, are therefore proposed. Moreover, the effect of water on the catalytic activity was studied. A moderate amount of water induced either by catalyst pretreatment at the proper temperature or deliberately dosed on the ZrPO materials achieves a maximum catalytic activity. The highest catalytic activity, i.e., 82{\%} of PG conversion and 92{\%} of EM selectivity, was obtained on ZrPO-0.75-500 that was dosed by 15 μmol water per 50 mg of the catalyst. It is concluded that ZrPO with a suitable combination of LAS and BAS is required to efficiently and selectively catalyze the conversion of α-keto aldehydes to α-hydroxy carboxylic acid derivatives. It is feasible, from a practical point of view, to tune the density of LAS and BAS on the catalysts to achieve a better catalytic performance.",
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Correlation between acidity and catalytic performance of mesoporous zirconium oxophosphate in phenylglyoxal conversion. / Xu, Haimei; Wang, Zichun; Miao, Zhichao; Zhu, Yuxiang; Marianov, Aleksei; Wang, Lizhuo; Castignolles, Patrice; Gaborieau, Marianne; Huang, Jun; Jiang, Yijiao.

In: ACS Sustainable Chemistry and Engineering, Vol. 7, No. 9, 06.05.2019, p. 8931-8942.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Correlation between acidity and catalytic performance of mesoporous zirconium oxophosphate in phenylglyoxal conversion

AU - Xu, Haimei

AU - Wang, Zichun

AU - Miao, Zhichao

AU - Zhu, Yuxiang

AU - Marianov, Aleksei

AU - Wang, Lizhuo

AU - Castignolles, Patrice

AU - Gaborieau, Marianne

AU - Huang, Jun

AU - Jiang, Yijiao

PY - 2019/5/6

Y1 - 2019/5/6

N2 - The one-step conversion of α-keto aldehydes to α-hydroxy carboxylic acids and their derivatives using solid acids is of great appeal in biomass utilization. In this work, ordered mesoporous zirconium oxophosphate (ZrPO) catalysts with tunable acidity were prepared and their catalytic performance was evaluated using phenylglyoxal (PG) conversion to ethyl mandelate (EM). The roles of Lewis acid sites (LAS) and Brønsted acid sites (BAS) of ZrPO were investigated by kinetic studies of PG conversion combined with temperature-programmed desorption of ammonia (NH3-TPD) and solid-state NMR characterizations. It is found that the ratio of LAS to BAS on the ZrPO plays a dominant role in this reaction. ZrPO-0.75-500, with a LAS/BAS ratio of 2.1, was found to be the best catalyst. The reaction pathways, i.e., the direct isomerization of PG to EM by LAS and via the formation of an intermediate hemiacetal by BAS, are therefore proposed. Moreover, the effect of water on the catalytic activity was studied. A moderate amount of water induced either by catalyst pretreatment at the proper temperature or deliberately dosed on the ZrPO materials achieves a maximum catalytic activity. The highest catalytic activity, i.e., 82% of PG conversion and 92% of EM selectivity, was obtained on ZrPO-0.75-500 that was dosed by 15 μmol water per 50 mg of the catalyst. It is concluded that ZrPO with a suitable combination of LAS and BAS is required to efficiently and selectively catalyze the conversion of α-keto aldehydes to α-hydroxy carboxylic acid derivatives. It is feasible, from a practical point of view, to tune the density of LAS and BAS on the catalysts to achieve a better catalytic performance.

AB - The one-step conversion of α-keto aldehydes to α-hydroxy carboxylic acids and their derivatives using solid acids is of great appeal in biomass utilization. In this work, ordered mesoporous zirconium oxophosphate (ZrPO) catalysts with tunable acidity were prepared and their catalytic performance was evaluated using phenylglyoxal (PG) conversion to ethyl mandelate (EM). The roles of Lewis acid sites (LAS) and Brønsted acid sites (BAS) of ZrPO were investigated by kinetic studies of PG conversion combined with temperature-programmed desorption of ammonia (NH3-TPD) and solid-state NMR characterizations. It is found that the ratio of LAS to BAS on the ZrPO plays a dominant role in this reaction. ZrPO-0.75-500, with a LAS/BAS ratio of 2.1, was found to be the best catalyst. The reaction pathways, i.e., the direct isomerization of PG to EM by LAS and via the formation of an intermediate hemiacetal by BAS, are therefore proposed. Moreover, the effect of water on the catalytic activity was studied. A moderate amount of water induced either by catalyst pretreatment at the proper temperature or deliberately dosed on the ZrPO materials achieves a maximum catalytic activity. The highest catalytic activity, i.e., 82% of PG conversion and 92% of EM selectivity, was obtained on ZrPO-0.75-500 that was dosed by 15 μmol water per 50 mg of the catalyst. It is concluded that ZrPO with a suitable combination of LAS and BAS is required to efficiently and selectively catalyze the conversion of α-keto aldehydes to α-hydroxy carboxylic acid derivatives. It is feasible, from a practical point of view, to tune the density of LAS and BAS on the catalysts to achieve a better catalytic performance.

KW - Brønsted acid sites

KW - Lewis acid sites

KW - Biomass utilization

KW - Mesoporous zirconium oxophosphate

KW - Solid-state NMR

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UR - http://purl.org/au-research/grants/arc/DP150103842

UR - http://purl.org/au-research/grants/arc/DP180104010

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DO - 10.1021/acssuschemeng.9b00989

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SP - 8931

EP - 8942

JO - ACS Sustainable Chemistry and Engineering

T2 - ACS Sustainable Chemistry and Engineering

JF - ACS Sustainable Chemistry and Engineering

SN - 2168-0485

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