Synthesis of Cu–Mg/ZnO catalysts and catalysis in dimethyl oxalate hydrogenation to ethylene glycol: enhanced catalytic behavior in the presence of a Mg<sup>2+</sup> dopant

Kong, Xiangpeng; Chen, Zheng; Wu, Yuehuan; Wang, Ruihong; Chen, Jiangang; Ding, Lifeng

doi:10.1039/c7ra09435c

Cited by 24 publications

(18 citation statements)

References 65 publications

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“…Furthermore, Chen, et al. reported that the Cu‐1Mg/ZnO catalyst with 1 wt% MgO loading synthesized from pure malachite phase structure significantly improved the dispersion status of Cu, which effectively promoted dimethyl oxalate hydrogenation to ethylene glycol . The theoretical explanations of the experimental observations are provided in the present work where the consequences of incorporation of Mg in Cu/Zn malachite has been studied in detail and the crucial observations in brief are as follows, (a) introducing Mg into malachite structure improves the structural stability, (b) relatively higher substitution ratio of Mg/Zn into malachite promotes better Cu dispersion status and (c) relevant electronic environments of Cu/Zn will be modified by the incorporation of Mg atoms, which affects their reducibility.…”

Section: Resultsmentioning

confidence: 64%

New Theoretical Insights into the Origin of Highly‐Effective Dispersion of Cu‐Based Catalysts As‐Synthesized Using Mg/Zn Doped Malachite as Precursors

Zheng

Narkhede

2019

ChemistrySelect

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The effect of Mg substitution into malachite and Zn doped malachite structure has been precisely modeled and theoretically investigated for energetic, geometrical and electronic properties based on density functional theory. The calculations were carried out by well‐tested code Cambridge Serial Total Energy Package while the Local Density Approximation was applied to describe the exchange‐correlation potential. The Mg substitution added to the structural stability owing to its smallest formation energy and the stability of ‐Cu‐O−Mg‐ bond provides well dispersed Cu species. In addition, Mg offers higher tendency to form more stable structure with Cu than Zn at high substitution ratio of Mg/Cu. The introduction of Mg further increases the net charges of Zn atoms and reduces the covalent characteristic of Zn−O bond. The densities of states supported the strengthening of covalent characteristic of Zn−O and Cu−O while Mg−O exhibited ionic characteristic with increasing Mg/Zn. Our calculations provide fundamental understanding of Cu/Mg/Zn system resulting in effective Cu dispersion and thermodynamically stable activity.

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Section: Resultsmentioning

confidence: 64%

New Theoretical Insights into the Origin of Highly‐Effective Dispersion of Cu‐Based Catalysts As‐Synthesized Using Mg/Zn Doped Malachite as Precursors

Zheng

Narkhede

2019

ChemistrySelect

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“…The high-temperature peak is attributed to the reduction of CuO particles interacting with ZnO. 29 The increase in reduction temperature after doping with Mg or La is ascribed to the strengthened interaction between Cu and the doped ZnO. The greatest increase in highest reduction temperature is observed for La-doped CZA (CZA: 260 °C, Mg-CZA: 268 °C, La-CZA: 286 °C).…”

Section: ■ Introductionmentioning

confidence: 99%

“…Mg is an isoelectronic ZnO dopant with a similar ionic radius. Mg was doped into ZnO to regulate its (i) electronic structure, (ii) surface oxygen defect, and (iii) metal–support interaction, , without affecting the morphology of ZnO. Similarly, La is an effective electronic promoter for introducing defects into ZnO without imposing significant morphological changes at a controlled level of doping .…”

Section: Introductionmentioning

confidence: 99%

Doping-Mediated Metal–Support Interaction Promotion toward Light-Assisted Methanol Production over Cu/ZnO/Al₂O₃

et al. 2021

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Many studies have demonstrated the feasibility of utilizing light-mediated electronic perturbations to regulate or promote the thermal catalytic conversion of CO2 to methanol. However, such studies are usually performed on pre-designed thermal catalysts with little regard to properties which govern the light-driven process. Herein, we investigate the promoting effect of two dopants with different intrinsic properties on metal–support interaction and catalytic performance. The promoting effects of Mg and La are assessed during thermal and light-assisted methanol synthesis over the Cu/ZnO/Al2O3 (CZA) catalyst. Photoenhancement factor increased from 138% (CZA) to 146 and 164%, respectively, for Mg- and La-doped catalysts. Enriched interfacial oxygen vacancies are tentatively determined as the predominant factor which channels the photogenerated electrons to the adsorbed formate species at the interface. X-ray photoelectron spectroscopy and temperature-programmed H2 reduction analyses also suggest a defect-mediated improvement in the Cu–ZnO interaction in the presence of both dopants. In addition, the La-doped catalyst enhanced methanol selectivity by modulating the adsorption states of intermediates, as shown by density functional theory and in situ diffuse reflectance infrared Fourier transform spectroscopy studies. This work illustrates the potential of improving light-driven processes by boosting the metal–support interfacial interaction.

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“…It is the world's second largest nutritional supplement for crops after nitrogen (Adnan et al, 2017). Mg and its compounds are widely used in a number of high-value industrial applications such as in the production of certain alloys and catalysts, and in the chemical, electronic, pharmaceutical and agricultural industries (Tran et al, 2013;Tran et al, 2016;Kong et al, 2017).…”

Section: Introductionmentioning

confidence: 99%

Biotransformation of struvite by Aspergillus niger: phosphate release and magnesium biomineralization as glushinskite

Suyamud

Ferrier

Csetényi

et al. 2020

Environmental Microbiology

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Summary Struvite (magnesium ammonium phosphate‐MgNH4PO4·6H2O), which can extensively crystallize in wastewater treatments, is a potential source of N and P as fertilizer, as well as a means of P conservation. However, little is known of microbial interactions with struvite which would result in element release. In this work, the geoactive fungus Aspergillus niger was investigated for struvite transformation on solid and in liquid media. Aspergillus niger was capable of solubilizing natural (fragments and powder) and synthetic struvite when incorporated into solid medium, with accompanying acidification of the media, and extensive precipitation of magnesium oxalate dihydrate (glushinskite, Mg(C2O4).2H2O) occurring under growing colonies. In liquid media, A. niger was able to solubilize natural and synthetic struvite releasing mobile phosphate (PO43−) and magnesium (Mg2+), the latter reacting with excreted oxalate resulting in precipitation of magnesium oxalate dihydrate which also accumulated within the mycelial pellets. Struvite was also found to influence the morphology of A. niger mycelial pellets. These findings contribute further understanding of struvite solubilization, element release and secondary oxalate formation, relevant to the biogeochemical cycling of phosphate minerals, and further directions utilizing these mechanisms in environmental biotechnologies such as element biorecovery and biofertilizer applications.

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Synthesis of Cu–Mg/ZnO catalysts and catalysis in dimethyl oxalate hydrogenation to ethylene glycol: enhanced catalytic behavior in the presence of a Mg²⁺ dopant

Abstract: Mg2+ doped nanoscale Cu–Mg/ZnO catalysts prepared by the co-precipitation method have been systematically characterized focusing on the amount of Mg2+ ions incorporated.

Cited by 24 publications

References 65 publications

New Theoretical Insights into the Origin of Highly‐Effective Dispersion of Cu‐Based Catalysts As‐Synthesized Using Mg/Zn Doped Malachite as Precursors

New Theoretical Insights into the Origin of Highly‐Effective Dispersion of Cu‐Based Catalysts As‐Synthesized Using Mg/Zn Doped Malachite as Precursors

Doping-Mediated Metal–Support Interaction Promotion toward Light-Assisted Methanol Production over Cu/ZnO/Al₂O₃

Biotransformation of struvite by Aspergillus niger: phosphate release and magnesium biomineralization as glushinskite

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Synthesis of Cu–Mg/ZnO catalysts and catalysis in dimethyl oxalate hydrogenation to ethylene glycol: enhanced catalytic behavior in the presence of a Mg2+ dopant

Abstract: Mg2+ doped nanoscale Cu–Mg/ZnO catalysts prepared by the co-precipitation method have been systematically characterized focusing on the amount of Mg2+ ions incorporated.

Cited by 24 publications

References 65 publications

New Theoretical Insights into the Origin of Highly‐Effective Dispersion of Cu‐Based Catalysts As‐Synthesized Using Mg/Zn Doped Malachite as Precursors

New Theoretical Insights into the Origin of Highly‐Effective Dispersion of Cu‐Based Catalysts As‐Synthesized Using Mg/Zn Doped Malachite as Precursors

Doping-Mediated Metal–Support Interaction Promotion toward Light-Assisted Methanol Production over Cu/ZnO/Al2O3

Biotransformation of struvite by Aspergillus niger: phosphate release and magnesium biomineralization as glushinskite

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Synthesis of Cu–Mg/ZnO catalysts and catalysis in dimethyl oxalate hydrogenation to ethylene glycol: enhanced catalytic behavior in the presence of a Mg²⁺ dopant

Doping-Mediated Metal–Support Interaction Promotion toward Light-Assisted Methanol Production over Cu/ZnO/Al₂O₃