Comparative study of CO2 hydrogenation to methanol on cubic bixbyite-type and rhombohedral corundum-type indium oxide

Yang, Bin; Li, Longtai; Jia, Ziye; Liu, Xiping; Zhang, Chunjie; Guo, Limin

doi:10.1016/j.cclet.2020.05.031

Cited by 44 publications

(21 citation statements)

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“…17,47,49−53 Subgap states are also observed which could be due to the presence of oxygen vacancies as a common feature in In 2 O 3 . 45,54,55 Upon the incorporation of Zn dopants, the E g value was decreased to ∼3.51 and ∼3.31 eV for LD-IZO and HD-IZO, respectively, which is in good agreement with previous reports. 44,45,56 Such obtained band gap energies are consistent with those acquired utilizing the scanning tunneling spectroscopy (STS) (Figure S8 and Note S1).…”

Section: Resultssupporting

confidence: 92%

“…Figure c presents the Tauc plots extracted from the optical absorption analysis of all three samples. The optical band gap ( E g ) is obtained by extrapolating the linear part of the (αhυ) 1/2 versus hυ plot. , The E g for intrinsic In 2 O 3 is found to be ∼3.63 eV which is close to the reported values from the literature. ,,− Subgap states are also observed which could be due to the presence of oxygen vacancies as a common feature in In 2 O 3 . ,, Upon the incorporation of Zn dopants, the E g value was decreased to ∼3.51 and ∼3.31 eV for LD-IZO and HD-IZO, respectively, which is in good agreement with previous reports. ,, Such obtained band gap energies are consistent with those acquired utilizing the scanning tunneling spectroscopy (STS) (Figure S8 and Note S1). The observed lower value of the energy band gap for LD-IZO is mostly owing to the localized states induced by the Zn dopants .…”

Section: Resultssupporting

confidence: 72%

“…It is also observed that the E f of LD-IZO shifts close to that of the conduction band maximum ( E c ) due to the injection of free electrons. Although the current literature is ambiguous regarding the exact mechanism of zinc doping of indium oxide, we consider that the substitution of Zn 2+ for In 3+ may result in the generation of additional oxygen vacancies in the In 2 O 3 host due to the charge difference. ,,,, Assuming that each oxygen vacancy donates two electrons to the conduction band, the overall electron concentration of IZO is therefore increased. On the other hand, Zn 2+ dopants are electrically not active due to the formation of neutral complexes with oxygen vacancies .…”

Section: Resultsmentioning

confidence: 99%

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Printable Single-Unit-Cell-Thick Transparent Zinc-Doped Indium Oxides with Efficient Electron Transport Properties

Jannat

Syed

et al. 2021

ACS Nano

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Ultrathin transparent conductive oxides (TCOs) are emerging candidates for next-generation transparent electronics. Indium oxide (In2O3) incorporated with post-transition-metal ions (e.g., Sn) has been widely studied due to their excellent optical transparency and electrical conductivity. However, their electron transport properties are deteriorated at the ultrathin two-dimensional (2D) morphology compared to that of intrinsic In2O3. Here, we explore the domain of transition-metal dopants in ultrathin In2O3 with the thicknesses down to the single-unit-cell limit, which is realized in a large area using a low-temperature liquid metal printing technique. Zn dopant is selected as a representative to incorporate into the In2O3 rhombohedral crystal framework, which results in the gradual transition of the host to quasimetallic. While the optical transmittance is maintained above 98%, an electron field-effect mobility of up to 87 cm2 V–1 s–1 and a considerable sub-kΩ–1 cm–1 ranged electrical conductivity are achieved when the Zn doping level is optimized, which are in a combination significantly improved compared to those of reported ultrathin TCOs. This work presents various opportunities for developing high-performance flexible transparent electronics based on emerging ultrathin TCO candidates.

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Section: Resultssupporting

confidence: 92%

Section: Resultssupporting

confidence: 72%

Section: Resultsmentioning

confidence: 99%

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Printable Single-Unit-Cell-Thick Transparent Zinc-Doped Indium Oxides with Efficient Electron Transport Properties

Jannat

Syed

et al. 2021

ACS Nano

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“… 14 − 16 Many efforts have been made to optimize Cu-based catalysts for selective CO 2 hydrogenation to CH 3 OH. 5 , 17 An important corollary of these studies is that tuning Cu–support interactions using other supports than alumina can mitigate some of these drawbacks. For example, zirconia (ZrO 2 ) has been widely investigated as a support with improved catalytic performance over alumina-supported catalysts.…”

Section: Introductionmentioning

confidence: 99%

“…The high activity of the Cu–ZnO-based catalysts in the reverse water gas shift (rWGS) reaction decreases the CH 3 OH selectivity . Moreover, deactivation of the Cu–ZnO-based catalysts is accelerated by the large amounts of water byproduct formed during CO 2 hydrogenation. − Many efforts have been made to optimize Cu-based catalysts for selective CO 2 hydrogenation to CH 3 OH. , An important corollary of these studies is that tuning Cu–support interactions using other supports than alumina can mitigate some of these drawbacks. For example, zirconia (ZrO 2 ) has been widely investigated as a support with improved catalytic performance over alumina-supported catalysts. − …”

Section: Introductionmentioning

confidence: 99%

Ni–In Synergy in CO₂ Hydrogenation to Methanol

et al. 2021

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Indium oxide (In 2 O 3 ) is a promising catalyst for selective CH 3 OH synthesis from CO 2 but displays insufficient activity at low reaction temperatures. By screening a range of promoters (Co, Ni, Cu, and Pd) in combination with In 2 O 3 using flame spray pyrolysis (FSP) synthesis, Ni is identified as the most suitable first-row transition-metal promoter with similar performance as Pd–In 2 O 3 . NiO–In 2 O 3 was optimized by varying the Ni/In ratio using FSP. The resulting catalysts including In 2 O 3 and NiO end members have similar high specific surface areas and morphology. The main products of CO 2 hydrogenation are CH 3 OH and CO with CH 4 being only observed at high NiO loading (≥75 wt %). The highest CH 3 OH rate (∼0.25 g MeOH /(g cat h), 250 °C, and 30 bar) is obtained for a NiO loading of 6 wt %. Characterization of the as-prepared catalysts reveals a strong interaction between Ni cations and In 2 O 3 at low NiO loading (≤6 wt %). H 2 -TPR points to a higher surface density of oxygen vacancy (O v ) due to Ni substitution. X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and electron paramagnetic resonance analysis of the used catalysts suggest that Ni cations can be reduced to Ni as single atoms and very small clusters during CO 2 hydrogenation. Supportive density functional theory calculations indicate that Ni promotion of CH 3 OH synthesis from CO 2 is mainly due to low-barrier H 2 dissociation on the reduced Ni surface species, facilitating hydrogenation of adsorbed CO 2 on O v .

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Recent Advances in Alloy Catalysts for CO₂ Hydrogenation to Methanol

Gao,

Wen,

Wang

et al. 2024

ChemCatChem

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The increasing anthropogenic carbon dioxide emissions (CO2) have a huge environmental impact, and CO2 emission reduction is already a common view in our society. Recently, selective hydrogenation of CO2 to methanol has attracted much attention because the process can effectively mitigate CO2 emissions and simultaneously produce high‐value‐added chemicals and fuels. The catalysts play a very important role in achieving high efficiency of CO2 to methanol. As one promising alternative, the alloy catalysts have demonstrated high performance in CO2 hydrogenation to methanol due to their unique geometry and electronic properties. Herein, we review the recent advances in alloy catalysts, including solid solution alloys and intermetallic compounds (mainly Cu‐based, In‐based, Ga‐based, and other alloy catalysts) for heterogeneous catalysis of CO2 hydrogenation to methanol. Moreover, the research ideas and development prospects of alloy catalysts for CO2 hydrogenation to methanol are overviewed to provide the ideas and references for the subsequent research on alloy catalysts for CO2 hydrogenation.

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Comparative study of CO2 hydrogenation to methanol on cubic bixbyite-type and rhombohedral corundum-type indium oxide

Cited by 44 publications

References 44 publications

Printable Single-Unit-Cell-Thick Transparent Zinc-Doped Indium Oxides with Efficient Electron Transport Properties

Printable Single-Unit-Cell-Thick Transparent Zinc-Doped Indium Oxides with Efficient Electron Transport Properties

Ni–In Synergy in CO₂ Hydrogenation to Methanol

Recent Advances in Alloy Catalysts for CO₂ Hydrogenation to Methanol

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Comparative study of CO2 hydrogenation to methanol on cubic bixbyite-type and rhombohedral corundum-type indium oxide

Cited by 44 publications

References 44 publications

Printable Single-Unit-Cell-Thick Transparent Zinc-Doped Indium Oxides with Efficient Electron Transport Properties

Printable Single-Unit-Cell-Thick Transparent Zinc-Doped Indium Oxides with Efficient Electron Transport Properties

Ni–In Synergy in CO2 Hydrogenation to Methanol

Recent Advances in Alloy Catalysts for CO2 Hydrogenation to Methanol

Contact Info

Product

Resources

About

Ni–In Synergy in CO₂ Hydrogenation to Methanol

Recent Advances in Alloy Catalysts for CO₂ Hydrogenation to Methanol