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Progress and Understanding on Catalysts with Well-defined Interface for Boosting CO2 Conversion

Binran Zhao ,  Yiyi Zhao ,  Peng Liu ,  Yulong Men ,  Xinyu Meng ,  Yunxiang Pan

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Citation:  Binran Zhao, Yiyi Zhao, Peng Liu, Yulong Men, Xinyu Meng, Yunxiang Pan. Progress and Understanding on Catalysts with Well-defined Interface for Boosting CO2 Conversion[J]. Chinese Journal of Structural Chemistry, 2022, 41(4): 220401. doi: 10.14102/j.cnki.0254-5861.2022-0024 shu

Progress and Understanding on Catalysts with Well-defined Interface for Boosting CO2 Conversion

English

  • INTRODUCTION

    Dramatically increasing emission of CO2 into atmosphere is the most serious challenge faced by mankind.[1] Converting CO2 into valuable chemicals like CH3OH via thermocatalysis, photocatalysis and electrocatalysis processes is the most promising way to alleviate CO2 emission.[1-3] Multi-component composite catalysts with well-defined interface have been widely explored for CO2 conversion.[1-5] The interface among the catalyst components can efficiently trigger the synergistic effects of the catalyst components, formation of highly dispersed catalytic active sites and flexible transfer of the reaction intermediates to the catalytic active sites (Figure 1).[1-5] Besides, the interface has been shown to provide catalytic active sites for CO2 adsorption and conversion.[6-8] This makes the activity, selectivity and stability of multi-component composite catalysts with well-defined interface much better than those obtained by using the catalyst components separately.[1-8] How to finely tune the catalyst interface has thereby been a hot topic. Common methods usually use calcination above 300 ⁰C, H2-reduction at temperature higher than 300 ⁰C, hydrothermal process and solvothermal process.[9-17] Under high temperatures, the catalyst structures can be easily destroyed, especially for porous catalysts, e.g. zeolites and metal-organic frameworks.[15-17] Moreover, harmful substances, e.g. acid, alkali and organic reagent, are usually used in the common methods.[9-15] Therefore, methods operated under mild conditions at low temperature without using harmful substances are highly desired for fabricating more efficient catalysts to enhance CO2 conversion.

    Figure 1

    Figure 1.  Schematic for the roles of catalyst interface in CO2 conversion.
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    A discharge technique, named as cold plasma, has been recognized as an excellent alternative to common methods for tuning the interface properties of multi-component catalysts for CO2 conversion.[18-22] Cold plasma is formed by ionizing a gas or a gas mixture, e.g. Ar, air, O2 and N2, by applying a voltage of 100–200 V on the electrodes of cold plasma equipment (Figure 2). Dielectric barrier discharge, glow discharge and radio frequency discharge are typical cold plasma.[18-22] Cold plasma contains a large amount of electrons which have energies ranging from 5 to 10 eV and move fast as well as cations and anions.[18-22] However, the temperature of cold plasma is lower than 200 ⁰C, and can be further lowered to room temperature by simply changing the operation conditions.[18-22] Although lower than 200 ⁰C, the energy of the electrons in cold plasma is so high that collisions of the electrons with substances can efficiently trigger various reactions, e.g. dissociation of metal salts into metal oxides, reduction of metal cations into metallic atoms, formation of strong chemical bonds at the interface among catalyst components, creation of oxygen vacancies and functional groups on catalyst surfaces, and doping metal and non-metal atoms into catalysts.[18-27] The relatively low temperature of cold plasma can well maintain the structural properties of catalysts, especially the porous structures. In the cold plasma process, in addition to the nontoxic working gases like Ar, air, O2 and N2, no harmful acids, alkalis and organic reagents are used. Moreover, the interface properties of catalysts can be finely tuned by simply changing the operation conditions of cold plasma, e.g. working gas, power, time and pressure.[18-27]

    Figure 2

    Figure 2.  (a) Schematic for the set-up of cold plasma. (b) Image taking during the preparation process of catalysts by using cold plasma.
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    The cold-plasma-prepared catalysts have unique interface properties, and thereby exhibit superior performances in CO2 conversion over the catalysts prepared by using the traditional methods.[18-32] In order to further extend the application of outstanding catalysts prepared by using cold plasma, a critical review on the progress in the area is highly desired. There have been many reviews on CO2 conversion, but these reviews paid very little attention to the cold-plasma-prepared catalysts. Herein, we discuss the progresses on the cold-plasma-prepared catalysts with well-defined interface for CO2 conversion, demonstrate the origins of the excellent catalytic performance and the reaction mechanisms, and propose the challenges and opportunities for further studies.

    SUPPORTED NOBLE METAL CATALYSTS

    Supported noble metal catalysts, formed by loading noble metal nanoparticles (e.g. Pt, Pd and Ir nanoparticles) on supports (e.g. metal oxides, zeolites and metal-organic frameworks), are the most widely explored catalysts for CO2 conversion.[33-35] The properties of the metal-support interface determine the features of noble metal nanoparticles, e.g. size, morphology, defects and crystal planes, and thus influence the features of catalytic active sites, e.g. amount, distribution and structure.[33-35] Efficiently controlling the properties of the metal-support interface is crucial for improving the performance of the supported noble metal catalysts in CO2 conversion. Traditional methods for preparing the supported noble metal catalysts mainly include two steps: (i) loading noble metal cations on supports, and (ii) reducing the noble metal cations by H2 at temperature higher than 300 ⁰C.[33-38] The reduction step by using H2 converts noble metal cations into noble metal atoms at zero valence state, and drives the transfer and combination of noble metal atoms to form noble metal nanoparticles, thus leading to the supported noble metal catalysts. But, the catalysts prepared by traditional methods show relatively weak metal-support interaction, thus suffering from serious aggregation of noble metal nanoparticles. Moreover, the high temperature of the H2-reduction step further promotes the aggregation of noble metal nanoparticles. Therefore, on the catalysts prepared by traditional methods, the noble metal nanoparticles easily aggregate into larger sizes, and thereby show mixed crystal structures, with crystal planes having lower catalytic activity and more defects.[33-35] This inevitably decreases the activity, selectivity and stability of catalysts in CO2 conversion.

    A cold-plasma-driven room-temperature H2-free reduction was developed for reducing noble metal cations into metallic states in the absence of H2 at temperature lower than 30 ⁰C.[39-47] In the cold-plasma-driven reduction, only Ar is used as the working gas of cold plasma. Collisions of the high-energy electrons of cold plasma with noble metal species (cations, atoms, clusters, nanoparticles) and supports lead to three aspects: (i) reducing noble metal cations into metallic states, (ii) promoting the transfer and combination of noble metal atoms to form nanoparticles, and (iii) creating bond interactions at metal-support interface. The low temperature of cold-plasma-driven reduction as well as the bond interactions formed at metal-support interface efficiently suppress the aggregation of noble metal nanoparticles, and create well-defined metal-support interface (Figure 3).[39-47] This results in highly dispersed noble metal nanoparticles which have more perfect crystal structure, more uniform morphology, smaller size and more perfect crystal planes with higher catalytic activity, as compared with the catalysts prepared by traditional H2-reduction (Figures 3 and 4).[39-47] For example, the sizes of noble metal nanoparticles on Pt/TiO2, Pd/Al2O3 and Ag/TiO2 prepared by the cold-plasma-driven reduction are about 4.0, 2.0 and 6.0 nm, respectively, smaller than those on the catalysts prepared by the traditional H2-reduction (about 7.0, 8.0 and 18.0 nm, respectively) (Figure 4).[39] Moreover, the properties of metal-support interface and noble metal nanoparticles can be finely tuned by simply changing the operation conditions of the cold-plasma-driven reduction e.g. time, pressure, power and content of the metal cations. For example, the size of Au nanoparticles increased from 3.2 to 19.4 nm by tuning the content of the Au cations during the cold-plasma-driven reduction (Figure 5).[40] Apart from the formation of well-defined metal-support interface, some oxygen atoms from the supports may move to the metal nanoparticles, thus producing an ultrathin oxide shell on the metal nanoparticles.[18-27] This can also help to suppress the aggregation of metal nanoparticles. With the cold-plasma-driven reduction, many efficient supported noble metal catalysts with well-defined metal-support interface have been fabricated, e.g. supported Au, Pt, Pd, Rh, Ir and Ag catalysts.[39-47]

    Figure 3

    Figure 3.  TEM images and size distributions of catalysts prepared by the cold-plasma-driven reduction: (a and b) Pd/Al2O3, (c and d) Ag/TiO2, (e and f) Au/TiO2. Reproduced with permission from Ref.[39]
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    Figure 4

    Figure 4.  Particle size of catalysts prepared by different methods. Reproduced with permission from Ref.[39]
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    Figure 5

    Figure 5.  TEM images and sizes of supported Au nanoparticles prepared under different cold plasma conditions: (a) 100 μM HAuCl4 with 100 μM Aβ16−20 aqueous solutions (100Au + 100Aβ16−20), (b) 200Au + 100Aβ16−20, (c) 500Au + 100Aβ16−20. Reproduced with permission from Ref.[40]
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    Zhao et al. applied the cold-plasma-driven reduction to prepare an Al2O3-supported Ir catalyst (Ir/Al2O3-P), and compared the structural properties and catalytic performance of Ir/Al2O3-P in producing syngas (CO + H2) from CO2-reforming of CH4 with those of the catalyst prepared by the traditional H2-reduction at 600 ⁰C for 3 h (Ir/Al2O3-H).[41] In CO2-reforming of CH4 at 750 ⁰C, Ir/Al2O3-P showed a CO2 conversion of 73% and a CH4 conversion of 67%, which were about twice higher than those on Ir/Al2O3-H (CO2: 36%, CH4: 33%).[41] The enhanced catalytic performance could be due to the well-defined Ir-Al2O3 interface on Ir/Al2O3-P. The well-defined Ir-Al2O3 interface suppressed the aggregation of Ir nanoparticles, thus leading to a higher Ir nanoparticle dispersion (83.95%), a smaller average Ir nanoparticle size (1.18 nm) and a larger active surface area (2.268 m2·g-1) on Ir/Al2O3-P, as compared with those on Ir/Al2O3-H (30.09%, 3.29 nm, 0.813 m2·g-1).[41] This resulted in abundant active Ir sites for dissociating CH4 into CHx species and H2. The well-defined Ir-Al2O3 interface provided abundant active sites for the adsorption and activation of CO2 to form more CO2δ- species.[48, 49] The well-defined Ir-Al2O3 interface facilitated the transfer of CHx species from Ir nanoparticles to the CO2δ- adsorbed at Ir-Al2O3 interface, and drove the reaction of CO2δ- with CHx to form CO and H2. The multiple roles of the well-defined Ir-Al2O3 interface could be the origin for the enhanced performance of Ir/Al2O3-P in CO2-reforming of CH4.

    By using cold plasma, Rui et al. fabricated a Pd-P/In2O3 catalyst.[42] In CO2 hydrogenation with H2, the cold-plasma-prepared Pd-P/In2O3 showed a CO2 conversion > 20%, a CH3OH selectivity > 70% and a space-time yield (STY) of CH3OH up to 0.89 gMeOH h-1·gcat-1, which are higher than those on Pd/In2O3 prepared by traditional method.[42] The well-defined Pd-In2O3 interface could be responsible for the better catalytic performance of Pd-P/In2O3. Due to the well-defined Pd-In2O3 interface, the Pd nanoparticles on Pd-P/In2O3 had an average size as small as 3.6 nm, and mainly exposed the Pd(111) plane which provided the catalytic active sites for H2 dissociation.[42] This led to more catalytic active Pd sites for H2 dissociation, thus producing abundant H atoms on Pd nanoparticles. The well-defined Pd-In2O3 interface facilitated the transfer of the H atoms from Pd nanoparticles to In2O3, and the reaction of H atoms with the O atoms of In2O3 created an appropriate amount of oxygen vacancies at the Pd-In2O3 interface.[42] A monodentate formate (HCOO) species was demonstrated to be a key intermediate for CH3OH production from the CO2 hydrogenation on Pd-P/In2O3.[42] The oxygen vacancies at the Pd-In2O3 interface promoted CO2 adsorption, activation and hydrogenation to form the key HCOO intermediate for CH3OH production, and stabilized HCOO for further hydrogenation.[42] This favored for the CH3OH production from CO2 hydrogenation on Pd-P/In2O3. The reverse water gas shift (RWGS) reaction was the main competitive reaction for CH3OH formation during CO2 hydrogenation.[42] The synergistic effects between Pd nanoparticles and In2O3 due to the well-defined Pd-In2O3 interface helped to suppress the RWGS reaction through limiting the formation of COOH groups on catalyst.[42] This was also benefit for producing CH3OH from CO2 hydrogenation on Pd-P/In2O3. Moreover, the more abundant H atoms formed on Pd nanoparticles as well as the flexible transfer of the H atoms from Pd nanoparticles to the CO2 adsorbed at the Pd-In2O3 interface efficiently lowered the activation barriers for CH3OH formation through the HCOO reaction route.[42] This further enhanced the CH3OH formation from CO2 hydrogenation on Pd-P/In2O3.

    Men et al. reported a Pt/film/In2O3 catalyst prepared by using the cold-plasma-driven reduction.[43] During CO2 hydrogenation on Pt/film/In2O3, a CO2 conversion of 37.0%, a CH3OH selectivity of 62.6% and a STY of CH3OH up to 0.355 gMeOH·h-1·gcat.-1 were achieved (Figure 6).[43] These were much better than those on Pt/In2O3-C prepared by the traditional H2-reduction method and commercial CuZnAl catalyst (Figure 6).[43] Due to the well-defined Pt-In2O3 interface, the Pt nanoparticles on Pt/film/In2O3 had a more perfect crystal structure, a higher dispersion and a smaller average size (3.5 nm), and exposed more Pt(111) plane which was more catalytic active to H2 adsorption and dissociation.[43] Different from Pt/film/In2O3, a serious aggregation of Pt nanoparticles was observed on Pt/In2O3-C, resulting in the average Pt nanoparticle size on Pt/In2O3-C as large as 10.2 nm.[43] Thereby, as compared with Pt/In2O3-C, there are more active Pt sites on Pt/film/In2O3 for dissociating H2 to form abundant H atoms. The well-defined Pt-In2O3 interface created more active sites for improving the adsorption and activation of CO2 on Pt/film/In2O3. In addition, as compared with those on Pt/In2O3-C, the transfer of H atoms from Pt nanoparticles to the CO2 adsorbed at Pt-In2O3 int-erface was more flexible due to the well-defined Pt-In2O3 interface on Pt/film/In2O3. The more abundant H atoms, improved CO2 adsorption and activation as well as the flexible transfer of H atoms promoted the formation of methoxy species (CH3O) which was a key species in producing CH3OH from CO2 hydrogenation, thus enhancing the CH3OH production from CO2 hydrogenation on Pt/film/In2O3.

    Figure 6

    Figure 6.  (a) CO2 conversion efficiency and CH3OH selectivity as well as (b) STY of CH3OH on different catalysts. Reproduced with permission from Ref.[43]
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    SUPPORTED TRANSITION METAL CATALYSTS

    The supported noble metal catalysts have superior activity, selectivity and stability to CO2 conversion. But the high price and scarce resource of noble metals limit the large-scale commercial applications of the supported noble metal catalysts. Supported transition metal catalysts, e.g. supported Ni, Co and Fe catalysts, which have low cost and abundant resource, are highly desired for CO2 conversion.[50-55] However, the activity, selectivity and stability of supported transition metal catalysts are still lower, and need further improvement. Traditional methods to prepare supported transition metal catalysts mainly include three steps: (i) loading transition metal salts (e.g. nickel nitrate) on the supports through wet impregnation, (ii) conducting calcination above 300 ⁰C to decompose the transition metal salts into transition metal oxides, and (iii) reducing the transition metal oxides by H2 at temperature higher than 300 ⁰C to form the supported transition metal catalysts.[50-55] Catalysts prepared by the traditional methods usually have weak metal-support interaction, and thereby suffer from transition metal nanoparticle aggregation.[50-55] The relatively high temperature of calcination and H2-reduction further promote the aggregation of transition metal nanoparticles. Thus, on catalysts prepared by using the traditional methods, the transition metal nanoparticles generally show mixed crystal structures, with the crystal planes having low catalytic activity and more defects.[50-55] This was proposed to be the origin for lower efficiency of the supported transition metal catalysts in CO2 conversion. Besides, for CO2 conversion, e.g. CO2-reforming of CH4, carbon deposition occurs easily, due to CO disproportionation and splitting of carbon-containing species like CH4.[50-55] The transition metal catalysts are poor in resisting to carbon deposition.[50-55] The deposited carbon atoms can incorporate into the lattice of transition metals to convert transition metals into transition metal carbides, and can insert into the metal-support interface to separate transition metal nanoparticles and supports (Figure 7).[56-59] The deposited carbon atoms can also accumulate around transition metal nanoparticles to wrap transition metal nanoparticles (Figure 7), thus hindering the adsorption and conversion of reactants on catalytic active sites.[56-59] The serious carbon deposition inevitably decreases the catalytic performance of the supported transition metal catalysts.

    Figure 7

    Figure 7.  Carbon deposition on Ni/Al2O3 catalyst during CO2-reforming of CH4. Reproduced with permission from Ref.[58]
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    A cold-plasma-assisted process has been developed to prepare the supported transition metal catalysts with well-defined interface for achieving more efficient CO2 conversion.[59-72] Different from supported noble metal catalysts, when using H2-free cold plasma to prepare supported transition metal catalysts, the high-energy electrons of cold plasma cannot reduce transition metal cations into metallic states. The cold-plasma-assisted preparation of the supported transition metal catalysts mainly includes three steps: (i) loading transition metal salts on supports through wet impregnation, (ii) treating the (transition metal salts)-support sample by cold plasma to decompose transition metal salts into transition metal oxides, and (iii) reduction of transition metal oxides by H2 at temperature higher than 300 ⁰C to form the supported transition metal catalysts. The second step with cold plasma plays two crucial roles. Firstly, collisions of the high-energy electrons of cold plasma with transition metal salts decompose transition metal salts into transition metal oxides. Secondly, collisions of the high-energy of electrons of cold plasma with transition metal oxide nanoparticles and supports create stronger bond interactions between transition metal oxide nanoparticles and supports, and tightly anchor transition metal oxide nanoparticles on supports (Figure 8).[60] Due to the stronger interactions between transition metal oxide nanoparticles and supports, the metal-support interface on the catalysts after H2 reduction is still well-defined, although the reduction temperature is higher than 300 ⁰C. This makes the transition metal nanoparticles on the catalysts prepared through the cold-plasma-assisted process exhibit perfect crystal structure, uniform morphology, smaller size and more crystal planes with higher catalytic activity. Therefore, the performance of the supported transition metal catalysts prepared by the cold-plasma-assisted process in CO2 conversion is better than those on the supported transition metal catalysts prepared by traditional methods, even better than those on the supported noble metal catalysts.

    Figure 8

    Figure 8.  TEM images of (a) NiO/Ta2O5 and (b) NiO/ZrO2 prepared by using the cold-plasma-assisted process. Reproduced with permission from Ref.[60]
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    Pan et al. fabricated a SiO2-supported Ni catalyst (P-Ni/SiO2) via the cold-plasma-assisted process, and compared the performance of P-Ni/SiO2 in CO2-reforming of CH4 with that of the C-Ni/SiO2 catalyst prepared by traditional method without cold plasma.[61] At 600 ⁰C, P-Ni/SiO2 showed CO2 and CH4 conversion of about 50% and 40%, respectively, which were higher than those on C-Ni/SiO2 (CO2: 40%, CH4: 25%). More importantly, P-Ni/SiO2 was much more efficient in suppressing carbon deposition than C-Ni/SiO2. This could be caused by the well-defined Ni-SiO2 interface on P-Ni/SiO2. Due to the well-defined Ni-SiO2 interface, the Ni nanoparticles on P-Ni/SiO2 showed a higher dispersion (17.0%), a smaller average size (5.9 nm), a larger active surface area (9.1 m2·g-1) and more Ni(111) planes, as compared with those on C-Ni/SiO2 (10.7%, 9.4 nm, 5.7 m2·g-1) (Figure 9).[61] Decomposition of CH4 (CH4 → C + H2) on Ni nanoparticle produced carbon atoms which were the source of carbon deposition.[61] The carbon atoms can react with CO2 to form CO (CO2 + C → 2CO).[61] This was the way to eliminate carbon from catalyst. The carbon formation-elimination balance determined the amount of the carbon deposited on catalyst, and was closely related to the rates of (CH4 → C + H2) and (CO2 + C → 2CO) reactions. If the (CO2 + C → 2CO) reaction proceeded more slowly than the (CH4 → C + H2) reaction, the carbon atoms precipitated and polymerized. The (CH4 → C + H2) reaction was sensitive to the structural properties of Ni nanoparticles. The Ni nanoparticles with more Ni(111) planes exposed are shown to be more efficient to suppress carbon formation from the (CH4 → C + H2) reaction, as compared with the Ni nanoparticles with more distortions and defects.[61] Due to the lower crystallinity and more defects of Ni nanoparticles on C-Ni/SiO2, the carbon formation and precipitation proceeded readily. Moreover, due to weak Ni-SiO2 interaction, the carbon atoms easily entered into the Ni-SiO2 interface on C-Ni/SiO2. This resulted in the serious carbon deposition on C-Ni/SiO2. Different from C-Ni/SiO2, the Ni nanoparticles on P-Ni/SiO2 had a more perfect crystallinity, less defects and more Ni(111) planes, thus suppressing the carbon formation from (CH4 → C + H2) reaction. Thereby, the carbon formation rate on P-Ni/SiO2 could be much lower than that on C-Ni/SiO2. In addition, the well-defined Ni-SiO2 interface created more abundant active sites for CO2 adsorption and activation to form more CO2δ- species.[48] CO2δ- had a higher activity to react with the carbon atoms formed from the (CH4 → C + H2) reaction, enhancing carbon elimination on P-Ni/SiO2.[48] Thus, P-Ni/SiO2 could have a higher carbon elimination rate than C-Ni/SiO2. The lower carbon formation rate but higher carbon elimination rate are responsible for the greatly enhanced ability of P-Ni/SiO2 in suppressing carbon deposition.

    Figure 9

    Figure 9.  HRTEM images of Ni nanoparticles on (a) C-Ni/SiO2 and (b) P-Ni/SiO2. Reproduced with permission from Ref.[61]
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    By using the cold-plasma-assisted preparation process, Yan et al. added CeO2 into Ni/SiO2 to form a Ni/CeO2-SiO2-P catalyst for CO2-reforming of CH4.[62] On the catalyst prepared by the traditional method without cold plasma (Ni/CeO2-SiO2-C), the Ni and CeO2 nanoparticles were separately dispersed on SiO2 to form Ni-SiO2 and CeO2-SiO2 interfaces, but there was no Ni-CeO2 interface (Figure 10).[62] On Ni/CeO2-SiO2-P, the CeO2 nanoparticles located at the Ni-SiO2 interface, and tightly interacted with both Ni nanoparticle and SiO2 support (Figure 10).[62] The intimate Ni-CeO2-SiO2 interface on Ni/CeO2-SiO2-P played crucial roles in CO2-reforming of CH4. Firstly, the intimate Ni-CeO2-SiO2 interface provided more abundant active sites for CO2 adsorption and activation to form more COδ- species.[62] This promoted the reaction of CO2δ- with the carbon atoms formed from the (CH4 → C + H2) reaction, thus increasing the carbon elimination rate on Ni/CeO2-SiO2-P. Secondly, the intimate Ni-CeO2-SiO2 interface anchored the Ni nanoparticles on support firmly, and suppressed the aggregation of Ni nanoparticles.[62] This made the Ni nanoparticles on Ni/CeO2-SiO2-P have more perfect crystallinity which can efficiently suppress the carbon formation from the (CH4 → C + H2) reaction. Therefore, the intimate Ni-CeO2-SiO2 interface suppressed carbon formation but promoted carbon elimination. This led Ni/CeO2-SiO2-P to have a higher ability in resisting to carbon deposition and a significantly improved stability in a long-term reaction (50 h).[62] Different from Ni/CeO2-SiO2-P, the catalytic performance of Ni/CeO2-SiO2-C decreased dramatically when conducting the CO2-reforming of CH4 for only 10 h, due to serious carbon deposition.[62] In-situ DRIFTs analyses were preformed to compare the mechanism of the CO2-reforming of CH4 on Ni/CeO2-SiO2-P with that on Ni/CeO2-SiO2-C.[62] On the DRIFTs spectra of Ni/CeO2-SiO2-C, bands attributed to CH4, CO, carbonate species (CO32-) and CO2δ- were observed.[62] On the DRIFTs spectra of Ni/CeO2-SiO2-P, besides CH4, CO, CO32- and CO2δ-, formate (HCOO) was also present, [62] indicating it could be formed as an important intermediate during the CO2-reforming of CH4 on Ni/CeO2-SiO2-P.[62] The formation of formate on Ni/CeO2-SiO2-P could be from the intimate Ni-CeO2-SiO2 interface. It has been revealed that the formation of (CO + H2) from the CO2-reforming of CH4 via the reaction with formate as an intermediate proceeded more easily, both thermodynamically and kinetically.[62] Thereafter, the intimate Ni-CeO2-SiO2 interface promoted the formation of formate to enhance the (CO + H2) production in CO2-reforming of CH4 on Ni/CeO2-SiO2-P.

    Figure 10

    Figure 10.  Proposed reaction pathways for the CO2-reforming of CH4 on (a) Ni/CeO2-SiO2-C and (b) Ni/CeO2-SiO2-P catalysts. Reproduced with permission from Ref.[62]
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    Jia et al. reported a Ni/ZrO2-P catalyst prepared by using the cold-plasma-assisted process for CO2 methanation.[63] On the catalyst fabricated through the traditional high-temperature calcination (Ni/ZrO2-C), Ni nanoparticles agglomerated on ZrO2 and the Ni lattice were difficult to distinguish due to the highly disordered crystal structure (Figure 11).[63] On Ni/ZrO2-P, Ni nanoparticles with an average size of about 10 nm were highly dispersed on ZrO2, more Ni(111) planes with a higher catalytic activity were exposed, and well-defined Ni-ZrO2 interface can be clearly seen (Figure 11).[63] The well-defined Ni-ZrO2 interface on Ni/ZrO2-P suppressed the aggregation of Ni nanoparticles during the CO2 methanation process, but serious aggregation of Ni nanoparticles occurred during the CO2 methanation process on Ni/ZrO2-C due to the weak Ni-ZrO2 interaction (Figure 11).[63] The well-defined Ni-ZrO2 interface on Ni/ZrO2-P created oxygen vacancies which provided catalytic active sites for CO2 adsorption and activation.[63] The conversion pathway of CO2 methanation on Ni/ZrO2-P was proposed as follows (Figure 12).[63] Adsorption and activation of CO2 on the oxygen vacancies at Ni-ZrO2 interface resulted in a CO3δ- species.[63] The Ni(111) planes promoted the H2 dissociation to form abundant H atoms. The H atoms can be easily transferred to the Ni-ZrO2 interface and reacted with CO3δ- to form a HCOOδ- species which was subsequently decomposed into CO.[63] The formed CO migrated to the Ni(111) planes and reacted with H atoms to form CH4 (Figure 12). The weak Ni-ZrO2 interaction made the amount of oxygen vacancies on Ni/ZrO2-C less than that on Ni/ZrO2-P. This led the adsorption of CO2 on Ni/ZrO2-C to be very weak, and decreased the activation degree of the adsorbed CO2, thus limiting the reaction of the adsorbed CO2 with H atoms. In addition, different from Ni/ZrO2-P, on Ni/ZrO2-C, due to the lack of Ni(111) plane, the dissociation of H2 into H atoms proceeded more difficultly. This further suppressed the hydrogenation of adsorbed CO2. These aspects led the catalytic performance of Ni/ZrO2-P in CO2 methanation to be much better than that of Ni/ZrO2-C. At 250 and 275 ⁰C, the CO2 conversion on Ni/ZrO2-P is 15.4% and 50.2%, respectively, which are much higher than those on Ni/ZrO2-C (6.1% and 15.2%).[63]

    Figure 11

    Figure 11.  TEM images of (a) Ni/ZrO2-P and (b) Ni/ZrO2-C. HRTEM images of (c and e) Ni/ZrO2-P and (d) Ni/ZrO2-C. TEM images of (f) used Ni/ZrO2-P after CO2 methanation and (g) Ni/ZrO2-C after CO2 methanation. Reproduced with permission from Ref.[63]
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    Figure 12

    Figure 12.  Proposed possible pathways for the CO2 methanation reaction on (a) Ni/ZrO2-P and (b) Ni/ZrO2-C catalysts. Reproduced with permission from Ref.[63]
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    By using cold plasma, Rui et al. fabricated a Ni/CeO2-P catalyst for CO2 methanation.[64] As compared with the Ni/CeO2-C catalyst prepared by traditional method, Ni/CeO2-P showed a much higher low-temperature activity to CO2 methanation. At 275 ⁰C, the CO2 conversion on Ni/CeO2-P catalyst was 82.4%, whereas that on Ni/CeO2-C was only 34.7%.[64] The CH4 generation rate and selectivity on Ni/CeO2-P were 100.3 μmol·gcat-1·s-1 and 99.5%, respectively.[64] These were better than those on Ni/CeO2-C. At the same CO2 conversion efficiency, the reaction temperature on Ni/CeO2-P was lower by 75 ⁰C than that on Ni/CeO2-C.[64] The enhanced catalytic performance of Ni/CeO2-P could be due to the well-defined Ni-CeO2 interface. The well-defined Ni-CeO2 interface provided more active sites for CO2 adsorption and activation.[64] The well-defined Ni-CeO2 interface made the size of Ni nanoparticles on Ni/CeO2-P smaller than that on Ni/CeO2-C, and thus created abundant active sites for H2 dissociation to form more H atoms.[64] The well-defined Ni-CeO2 interface facilitated the transfer of H atoms from Ni nanoparticles to CO2 adsorbed at Ni-CeO2 interface, thus promoting the reaction of the H atoms with the CO2 adsorbed at the Ni-CeO2 interface. It was the multiple roles of Ni-CeO2 interface that resulted in the enhanced CH4 production from the hydrogenation of CO2 on Ni/CeO2-P.[64]

    Apart from Ni-based catalysts, cold plasma was also efficient for preparing many other supported transition metal catalysts, e.g. supported Co and Fe catalysts, as well as other types of noble-metal-free catalysts for CO2 conversion.[56, 65-72] For instance, Zheng et al. formed an In2S3-NiS modified MoO3@MoS2 catalyst (INS/MoO3@MoS2) by using cold plasma.[65] Different from the catalysts prepared through the traditional method in the absence of cold plasma, tight interface among In2S3, NiS, MoS2 and MoO3 were formed on INS/MoO3@MoS2.[65] The rigorous In2S3-NiS-MoS2-MoO3 interface created well-defined interfacial heterojunctions, and thus promoted the CH4 production from the photocatalytic reduction of CO2, with the CH4 product rate as high as 49.11 μmol·g-1·h-1.[65] Due to the formation of the rigorous In2S3-NiS-MoS2-MoO3 interface, some additional states were created between the conduction band and the valence band of the catalyst.[65] This helped to extend the wavelength range of the light absorbed by catalyst.[65] The rigorous In2S3-NiS-MoS2-MoO3 interface also favored for the separation and transfer of the photogenerated charge carriers, thus promoting more photogenerated electrons for surface reactions.[65] Besides, due to the tight In2S3-NiS-MoS2-MoO3 interface, more catalytic active sites were formed for the adsorption and conversion of reactants, thus resulting in more activated reactants for surface reactions.[65] The improved light absorption, promoted charge separation and more catalytic active sites for reactant adsorption and conversion enhanced the production of CH4 from the photocatalytic reduction of CO2 on INS/MoO3@MoS2.

    CONCLUSIONS AND PERSPECTIVE

    In summary, the interface on multi-component catalysts triggers valuable synergistic effects and multifunctional properties, flexible transfer of active species and reaction intermediates, and highly dispersed catalytic active sites (e.g. noble metal and transition metal nanoparticles), thus playing crucial roles in enhancing the CO2 conversion efficiency. Cold plasma has been demonstrated to be an excellent and simple strategy to finely tune catalyst interface properties for improving CO2 conversion efficiency. The most attractive point of the cold plasma process is that the energy of the electrons in cold plasma is as high as 5–10 eV but the operation temperature of cold plasma is lower than 200 ⁰C. By simply changing the conditions of cold plasma, e.g. time, power and pressure, the operation temperature of cold plasma can be lowered to room temperature. Thus, when conducting cold plasma for preparing catalysts, the catalyst interface properties can be efficiently tuned. At the same time, the structural features of catalysts can be well maintained, e.g. the porous structures. The cold-plasma-prepared catalysts exhibit superior performance in CO2 conversion over the catalysts prepared by the traditional methods, due to their unique interface properties. However, there are still several issues on cold-plasma-prepared catalysts required to be further studied detailedly.

    Firstly, better understanding on the exact roles of the catalyst interface in CO2 conversion is necessary. There have been a large amount of studies focusing on the influence of catalyst interface on CO2 conversion, including both experiments and theoretical calculations. The interface sites were revealed to be the active sites for CO2 adsorption and activation. However, the exact site for the conversion of adsorbed CO2 is still unclear. Some studies proposed that other reactants transfer to the interface sites and react with the adsorbed CO2, while some studies reported that the adsorbed CO2 was firstly activated into intermediates like formate and CO at the interface sites, and then the intermediates migrated to the sites on the supported metal nanoparticles and react with other reactants. More detailed studies have to be conducted, especially experiments like in-situ FTIR and theoretical calculations. But, due to the high complexity of the reaction, the construction of an ideal model matching well with the real system is still a challenge. In addition, during the reaction process, the interface properties could change, due to the interaction of CO2 with the interface sites. More studies have to be done for clarifying the changes of the interface properties during the reaction process.

    Secondly, better understanding on the exact mechanism of the change in interface properties during the cold plasma process is necessary. Collisions of the high-energy electrons in cold plasma with the catalyst components were proposed to be the main drive to create stronger interactions among the catalyst components, thus fabricating the well-defined interface properties. However, in addition to the electrons, a large number of other species, e.g. atoms, anions, radicals and cations, also exist in cold plasma. The roles of different species produced from cold plasma in tuning the catalyst interface properties have to be more detailedly studied, by using both experimental and theoretical observations. However, because cold plasma is a very complex system, studies on it need knowledge not only from chemistry and material but also from many other areas like physics, engineering and machine.

    Due to the outstanding performance of cold-plasma-prepared catalysts in CO2 conversion, finely tuning the interface properties by using cold plasma has stimulated numerous studies. We believe that, due to the continued efforts on optimizing the equipments and operation conditions of cold plasma as well as the worldwide attention on CO2 utilization, massive application of the cold-plasma-prepared catalysts in industry will come true in the near future.


    ACKNOWLEDGEMENTS: This work is supported by the National Natural Science Foundation of China (No. 21922807 and 22078193), Double Thousand Plan of Jiangxi Province (461654, jxsq2019102052) and Shaanxi Provincial Key Research and Development Program (No. 2020ZDLGY11-06). COMPETING INTERESTS
    The authors declare that they have no competing interests.
    http://manu30.magtech.com.cn/jghx/EN/10.14102/j.cnki.0254-5861.2022-0024
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  • Figure 1  Schematic for the roles of catalyst interface in CO2 conversion.

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    Figure 2  (a) Schematic for the set-up of cold plasma. (b) Image taking during the preparation process of catalysts by using cold plasma.

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    Figure 3  TEM images and size distributions of catalysts prepared by the cold-plasma-driven reduction: (a and b) Pd/Al2O3, (c and d) Ag/TiO2, (e and f) Au/TiO2. Reproduced with permission from Ref.[39]

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    Figure 4  Particle size of catalysts prepared by different methods. Reproduced with permission from Ref.[39]

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    Figure 5  TEM images and sizes of supported Au nanoparticles prepared under different cold plasma conditions: (a) 100 μM HAuCl4 with 100 μM Aβ16−20 aqueous solutions (100Au + 100Aβ16−20), (b) 200Au + 100Aβ16−20, (c) 500Au + 100Aβ16−20. Reproduced with permission from Ref.[40]

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    Figure 6  (a) CO2 conversion efficiency and CH3OH selectivity as well as (b) STY of CH3OH on different catalysts. Reproduced with permission from Ref.[43]

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    Figure 7  Carbon deposition on Ni/Al2O3 catalyst during CO2-reforming of CH4. Reproduced with permission from Ref.[58]

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    Figure 8  TEM images of (a) NiO/Ta2O5 and (b) NiO/ZrO2 prepared by using the cold-plasma-assisted process. Reproduced with permission from Ref.[60]

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    Figure 9  HRTEM images of Ni nanoparticles on (a) C-Ni/SiO2 and (b) P-Ni/SiO2. Reproduced with permission from Ref.[61]

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    Figure 10  Proposed reaction pathways for the CO2-reforming of CH4 on (a) Ni/CeO2-SiO2-C and (b) Ni/CeO2-SiO2-P catalysts. Reproduced with permission from Ref.[62]

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    Figure 11  TEM images of (a) Ni/ZrO2-P and (b) Ni/ZrO2-C. HRTEM images of (c and e) Ni/ZrO2-P and (d) Ni/ZrO2-C. TEM images of (f) used Ni/ZrO2-P after CO2 methanation and (g) Ni/ZrO2-C after CO2 methanation. Reproduced with permission from Ref.[63]

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    Figure 12  Proposed possible pathways for the CO2 methanation reaction on (a) Ni/ZrO2-P and (b) Ni/ZrO2-C catalysts. Reproduced with permission from Ref.[63]

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  • 发布日期:  2022-04-08
  • 收稿日期:  2022-02-05
  • 接受日期:  2022-02-22
通讯作者: 陈斌, bchen63@163.com
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