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Article

Co Cluster-Modified Ni Nanoparticles with Superior Light-Driven Thermocatalytic CO2 Reduction by CH4

by
Mei Li
1,
Yuhua Zhang
2,
Na Sun
2,
Dan Cheng
2,
Peng Sun
2 and
Qian Zhang
2,*
1
School of Life Science and Technology, Shandong Second Medical University, Weifang 261053, China
2
School of Pharmacy, Shandong Second Medical University, Weifang 261053, China
*
Author to whom correspondence should be addressed.
Molecules 2024, 29(22), 5338; https://doi.org/10.3390/molecules29225338
Submission received: 17 October 2024 / Revised: 10 November 2024 / Accepted: 11 November 2024 / Published: 13 November 2024
(This article belongs to the Special Issue Design, Synthesis and Applications of Novel Transition Metal Catalysts)
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Abstract

:
Excessive fossil burning causes energy shortages and contributes to the environmental crisis. Light-driven thermocatalytic CO2 reduction by methane (CRM) provides an effective strategy to conquer these two global challenges. Ni-based catalysts have been developed as candidates for CRM that are comparable to the noble metal catalysts. However, they are prone to deactivation due to the thermodynamically inevitable coking side reactions. Herein, we reported a novel Co-Ni/SiO2 nanocomposite of Co cluster-modified Ni nanoparticles, which greatly enhance the catalytic durability for light-driven thermocatalytic CRM. It exhibits high production rates of H2 (rH2) and CO (rCO, 22.8 and 26.7 mmol min−1 g−1, respectively), and very high light-to-fuel efficiency (ƞ) is achieved (26.8%). Co-Ni/SiO2 shows better catalytic durability than the referenced catalyst of Ni/SiO2. Based on the experimental results of TG-MS, TEM, and HRTEM, we revealed the origin of the significantly enhanced light-driven thermocatalytic activity and durability as well as the novel photoactivation. It was discovered that the focused irradiation markedly reduces the apparent activation energy of CO2 on the Co-Ni/SiO2 nanocomposite, thus significantly enhancing the light-driven thermocatalytic activity.

1. Introduction

The rapid consumption of fossil fuels accompanied by population growth not only exacerbated the energy crisis, but also caused the excessive emissions of CO2 (greenhouse gas), leading to a critical greenhouse effect [1,2]. The photocatalytic reduction of CO2 driven by inexhaustible solar energy was an effective solution to the above-mentioned issues, which attracted wide attention [3,4,5,6,7]. However, the photocatalytic approach suffers from a low fuel production rate and low light-to-fuel efficiency (η).
In recent years, light-driven thermocatalytic (photothermocatalytic) CO2 reduction with CH4 [8,9,10,11,12,13,14,15,16,17,18,19], H2 [20,21] and H2O [22,23,24] has been considered as a promising approach, as it takes into account the advantages of the low energy consumption of photocatalysis and the high catalytic activity of thermocatalysis. Among several CO2 reduction approaches, light-driven thermocatalytic CRM is a prospective option on account of the high conversion rate of CO2 and CH4 to syngas and the achievement of solar-to-chemical energy conversion [25,26,27,28,29,30,31,32,33,34,35]. In the meantime, VIII group metal catalysts were reported to exhibit catalytic activity for light-driven thermocatalytic CRM. Among the catalysts, non-precious metal catalysts, such as Ni-based catalysts, have attracted great interest as a result of their low price, availability, and superior initial activity in contrast to the noble metal catalysts [8,9,18,19,36,37,38]. However, Ni-based catalysts are prone to severe deactivation which restrict their practical applications. As the coking deposition side reactions (CO disproportionation and CH4 dissociation) are thermodynamically favorable [39,40,41], the immediate concern is to exploit new Ni-based catalysts that can dynamically suppress carbon deposition. Therefore, these great challenges for the rational design of Ni-based catalysts are urgent to be tackled. Recently, there are several approaches that have been provided to significantly inhibit the carbon deposition on Ni-based catalysts [11,15,42,43,44,45,46,47], including modifying the surface of Ni nanoparticles with MgO clusters [42] or CeO2 clusters [43], by which the oxidation of carbon species can be accelerated.
Herein, we prepared a Co-Ni/SiO2 nanocomposite of Co cluster-modified Ni nanoparticles, which greatly boost the activity and durability of the nanocomposite for light-driven thermocatalytic CRM. It exhibits high production rates of H2 (rH2) and CO (rCO, 22.8 and 26.7 mmol min−1 g−1, respectively). The light-to-fuel efficiency (η) of the catalyst is as high as 26.8%. The high yield production rate originates from effective photothermal conversion and photoactivation induced by light irradiation. It was found that Co cluster modification of the Ni nanoparticles considerably enhances their light-driven thermocatalytic durability. Based on the experimental results, we delved into the origin of the excellent durability and photoactivation in the nanocomposite.

2. Results and Discussion

2.1. Catalyst Characterization

ICP (Inductively Coupled Plasma) analysis revealed that the Ni loadings of Co-Ni/SiO2 and Ni/SiO2 were 10.73 and 9.89 wt%, respectively. The XRD (X-ray diffraction) pattern showed that Ni exists in a crystalline metallic Ni phase (PDF70-1849) both in Co-Ni/SiO2 and Ni/SiO2, while silica exists in an amorphous phase (Figure 1a). No diffraction peaks for Co species can be observed in Co-Ni/SiO2, which is mainly ascribed to the low content or the amorphous status of the Co species. The average diameters of the metallic Ni nanoparticles in Co-Ni/SiO2 and Ni/SiO2, calculated according to the Scherrer formula (L = 0.89λ/βcosθ), were 4.5 and 4.1 nm, respectively. The TEM (Transmission Electron Microscopy) image (Figure 1b) and HAADF-STEM image (Figure 1e) showed that Ni nanoparticles were well dispersed on the amorphous silica in Co-Ni/SiO2. HRTEM (High-Resolution Transmission Electron Microscopy) (Figure 1c) and high-resolution HAADF-STEM (High-Angle Annular Dark-Field Scanning Transmission Electron Microscopy) (Figure 1f) images show that the Ni nanoparticles with a lattice spacing of 0.203 nm corresponding to the (111) facets were surrounded by the amorphous silica, but no lattice fringe attributed to the Co nanoparticles can be found in the field. HAADF-STEM images with element mapping were used to characterize the element distribution of Ni, Co, Si, and O in the Co-Ni/SiO2 sample. As shown in Figure S1, the Ni nanoparticles were surrounded by Co clusters and uniformly distributed on the SiO2. This result, together with the XRD results, indicate that Co species exist in an amorphous state. The TEM and HRTEM images of Ni/SiO2 showed that the Ni nanoparticles were well dispersed on the SiO2 with a lattice spacing of 0.203 nm corresponding to the (111) facets (Figure S2). XPS (X-ray photoelectron spectroscopy) showed that Ni presents as Ni2+ and Ni0 species in Co-Ni/SiO2 (Figure 1d). The presence of Ni2+ was ascribed to the oxidation of Ni species by the air, and the molar ratio of Ni0/Ni2+ was estimated to be 0.26. Si and Co exist in the form of Si4+ and Co0 (Figure S3), and the slight positive shifts of the Co0 peaks in binding energy were mainly attributed to the strong electron interactions of the closely contacted Ni and Co (Figure S3b). The N2 adsorption studies showed that the Brunauer–Emmett–Teller (BET) surface area of Co-Ni/SiO2 and Ni/SiO2 were 286.8 and 297.2 m2 g−1, respectively (Figure S4).

2.2. Light-Driven Thermocatalytic CRM Activity

The light-driven thermocatalytic CRM activity of the catalysts were conducted in a hand-made reactor with a quartz window as shown in Figure S1. The heat source was provided by a 500 W Xe lamp. Pure SiO2 has no catalytic activity for CRM, while Co-Ni/SiO2 exhibits extraordinary catalytic activity under focused UV-Vis-IR irradiation (Figure 2a). The H2 and CO production rates (rH2, rCO) of the Co-Ni/SiO2 catalyst reached 22.8 and 26.7 mmol min−1 g−1, respectively (Figure 2b), which are higher than that of Ni-/SiO2 (rH2 and rCO were 1.4 and 4.9 mmol min−1 g−1, respectively).
CRM is a strongly endothermic reaction (ΔH298 = 247.0 KJ mol−1). The high rH2 and rCO values of Co-Ni/SiO2 indicate that efficient light-to-fuel conversion occurred as the light-driven thermocatalytic CRM is merely driven by focused UV-Vis-IR irradiation.
The light-to-fuel efficiency (η) of Co-Ni/SiO2 for CRM under focused UV-Vis-IR irradiation reached a high value of 26.8% (Figure 2c), which is far higher than that of Ni/SiO2 (1.8%). In addition, Co-Ni/SiO2 also showed high catalytic activity for CRM under visible-infrared or infrared irradiation (Figure S5). Under vis-IR irradiation (λ > 420 nm), Co-Ni/SiO2 showed higher rH2 and rCO values of 16.4 and 21.2 mmol min−1 g−1, with an ƞ of 25.5%. Even under focused infrared irradiation (λ > 690 nm), Co-Ni/SiO2 still demonstrated good catalytic CRM activity, with an η of 18.1% (Figure 2d).

2.3. Light-Driven Thermocatalytic Durability

The long-term light-driven thermocatalytic CRM durability of Co-Ni/SiO2 was performed under focused UV-Vis-IR irradiation. As shown in Figure 3a, the rH2 and rCO at 96 h were 22.8 and 25.9 mmol min−1 g−1, which were identical to the initial activity at 1 h (Figure 3a). This result indicates that Co-Ni/SiO2 exhibits superior light-driven thermocatalytic CRM durability. On the contrary, Ni/SiO2 showed much lower catalytic activity than Co-Ni/SiO2 under the same reaction conditions (Figure 3b). Its rH2 and rCO at 1 h were 1.4 and 4.9 mmol min−1 g−1, respectively. Upon extending the irradiation time to 4 h, the rH2 and rCO quickly decreased to 0.2 and 1.8 mmol min−1 g−1, respectively. The reason for this rapid deactivation of Ni/SiO2 is the carbon (produced by CH4 dissociation and CO disproportionation at high temperatures) deposited on the surface of the Ni nanoparticles, which covered the active sites.

2.4. Origin of the Superior Light-Driven Thermocatalytic Durability

To delve into why the Co-Ni/SiO2 nanocomposite exhibits superior light-driven thermocatalytic CRM durability, TG-MS (Thermogravimetric Mass Spectrometry), TEM, and HRTEM were employed to characterize the used Co-Ni/SiO2 and Ni/SiO2 samples after the durability tests. As shown in the TG-MS profiles, the weight loss of the Co-Ni/SiO2 and Ni/SiO2 samples were 42.96 and 75.10%, respectively (Figure 3c,d), owing to the combustion of carbon. The rate of carbon deposition (rC) for the Co-Ni/SiO2 and Ni/SiO2 samples were calculated to 1.25 × 10−2 and 0.23 gC gcatal−1 h−1, respectively. The results of TEM also confirmed that there are more carbon nanofibers that can be observed in the used Ni/SiO2 sample than the used Co-Ni/SiO2 sample (Figure S6a,c). The HRTEM image showed that there was no carbon deposition on the Ni nanoparticles in Co-Ni/SiO2 (Figure S6b). On the contrary, severe deposition of graphite carbon with a lattice spacing of 0.340 nm corresponding to the (002) facets on the surface of Ni nanoparticles in Ni/SiO2 can be observed (Figure S6d), leading to the fast deactivation. This reveals the Co cluster modification of Ni nanoparticles in Co-Ni/SiO2 could inhibit the carbon deposition on the Ni nanoparticles as compared to Ni/SiO2, thus significantly enhancing the light-driven thermocatalytic durability. This result can be attributed to the modification of Ni by the Co cluster, which dilutes the surface atoms of Ni and prevents coke nucleation, making it more difficult for carbon atoms to bond.

2.5. The Function of Light

2.5.1. Heating Role

To reveal the function of focused irradiation during the light-driven thermocatalytic CRM, the optical absorption of Co-Ni/SiO2 and Ni/SiO2 were measured. As shown in Figure 4a, both Co-Ni/SiO2 and Ni/SiO2 demonstrate strong absorption from 240 to 2400 nm, which arises from the surface plasma absorption of the metallic Ni nanoparticles [48]. The photocatalytic CRM activity of the Co-Ni/SiO2 sample at near ambient temperatures under irradiation was performed. No detectable CO and H2 are produced, indicating that the CRM process cannot be driven by light irradiation at near-room temperature (Figure 4b). This result suggests that the highly effective catalytic activity of Co-Ni/SiO2 under focused irradiation arises from effective photothermal conversion.
Under focused irradiation, the temperature of the catalysts quickly increased to a steady temperature (Tst) as a result of the surface plasma absorption of metallic Ni nanoparticles and the infrared heating effect. The Tst values of the Co-Ni/SiO2 and Ni/SiO2 samples and the empty sample holder were 722, 698, and 650 °C, respectively (Figure 4c). The thermocatalytic CRM then proceeds at a high temperature. The high Tst value of the empty sample holder suggests that the infrared heating effect has as a critical role in raising the surface temperature of the samples.
Under focused visible-infrared and infrared irradiation (λ > 420, 560, and 690 nm), the Co-Ni/SiO2 sample reached its Tst of 680, 642, and 598 °C, respectively (Figure S7). In addition, the light-driven thermocatalytic CRM can proceed under focused irradiation of UV-Vis-IR, visible-infrared light, and near infrared light.

2.5.2. Photoactivation

To further reveal whether the light plays another role in the light-driven thermocatalytic CRM, the thermocatalytic activity of Co-Ni/SiO2 in the dark for CRM was measured at 722 °C as well as the Tst under focused irradiation. As shown in Figure 3a, its thermocatalytic activity was lower than that of focused irradiation. Under focused light irradiation, the rH2 and rCO at the first 1 h were promoted by 5.7 and 5.9 times, respectively, in comparison with those in the dark. This result indicates that the light not only plays a heating role but also induces photoactivation as the focused irradiation light can significantly promote the catalytic activity.
To probe into the photoactivation, the catalytic CRM activity of Co-Ni/SiO2 at different temperatures in the dark and under focused UV-Vis-IR irradiation were evaluated. The catalytic CRM activity of Co-Ni/SiO2 was greatly enhanced under focused irradiation compared with those in the dark (Figure 5a,b). However, Co-Ni/SiO2 has no photocatalytic activity under irradiation at near-room temperature, Therefore, the significant enhancement of the catalytic CRM activity under focused irradiation can be attributed to the photoactivation effect in addition to the efficient photothermal conversion.
To deeply reveal the photoactivation, we drew a diagram of ln(rCO2) vs. 1/T based on the rCO2 data of Co-Ni/SiO2 at different temperatures under focused irradiation and in the dark. As shown in Figure 5c, there is a good linear relationship between ln(rCO2) vs. 1/T. The apparent activation energy (Ea) was calculated by means of the Arrhenius equation (k = Ae−Ea/RT). The Ea of CO2 on Co-Ni/SiO2 was 89.2 kJ mol−1 in the dark, but under focused irradiation, the Ea of CO2 was remarkably reduced to 69.6 kJ mol−1. This result demonstrates that photoactivation facilitates the catalytic CRM activity of Co-Ni/SiO2 by reducing the Ea directly.

3. Materials and Methods

3.1. Catalyst Synthesis

Co-Ni/SiO2 nanocomposite: Na2SiO3.9H2O (25.578 g) and deionized water (85 mL) were stirred for 15 min, then the diluted HNO3 solution (the volume ratio of HNO3 to deionized water was 1:6) was added dropwise to the mixed solution under magnetic stirring until the vitreous products reached a pH of ~6. A mixed solution of Ni(NO3)2 (2.6173 g), Co(NO3)2 (0.2911 g), and deionized water (14 mL) was added dropwise to the vitreous products under magnetic stirring, then the aqueous ammonia solution (6 mL; the volume ratio of concentrated ammonia solution to deionized water was 1:5) was added dropwise to mixed solution. The mixture was kept at 90 °C for 24 h sealed by polyethylene film after being filtered, washed, dried, and grinded. The obtained powder was pre-reduced with 5.0 vol% H2/Ar (25 mL min−1) at 700 °C for 1 h to obtain Co-Ni/SiO2.
SiO2 sample: The pure SiO2 sample was prepared using a similar procedure with that of the above Co-Ni/SiO2 nanocomposite except that there was no addition of Ni(NO3)2·6H2O and Co(NO3)2.6H2O.
Ni/SiO2 sample: The production method of Ni/SiO2 sample was consistent with those of Co-Ni/SiO2 nanocomposite, except for the aqueous ammonia solution by NaOH aqueous solution (dissolved 0.48 g of NaOH with 10.0 g of deionized water).

3.2. Characterization

XRD patterns of the samples were obtained on a Rigaku (Shimadzu, Tokyo, Japan) Dmax X-ray diffractometer equipped with Cu Kα radiation. TEM images and energy-dispersive X-ray spectrographs (EDX) were acquired on a JEM-ARM200F electron microscope (Thermo Fisher Scientifitic, Waltham, MA, USA), while the specific surface areas of the samples were measured by N2 adsorption at −196 °C on an ASAP2020 instrument (Micrometer, Saint Louis, MO, USA). XPS spectra were recorded on an ESCALAB 250Xi X-ray photoelectron spectrometer using Mg Kα radiation (Perkin Elmer, Waltham, MA, USA). Thermogravimetric/mass spectrometry (TG-MS) analysis of the used sample after reaction was taken on a NETZSCH (Selb, Germany) STA449F3 thermal analyzer connected to a QMS403 mass spectrometer. Diffuse reflectance UV-visible-infrared absorption (DRUV-Vis-IR) spectra were acquired on a Lambda 750S spectrophotometer (Perkin Elmer, Waltham, MA, USA).

3.3. Light-Driven Thermocatalytic and Photocatalytic CRM Tests

The light-driven thermocatalytic CRM activity and durability of the samples for CRM under UV-Vis-IR irradiation from 500 W Xe lamp were assessed in a hand-made reactor equipped with quartz window (Scheme S1). A total of 0.0025 g of the sample was filled into the reactor, and a feed stream of 20.3–20.3–59.4 vol% CH4-CO2-Ar was flowed into the reactor at a flow rate of 90.5 mL min−1 controlled by a gas mass flow meter (S49-31MT). Gas-chromatography (GC-9560) was employed to determine the reactants and products.
The light-to-fuel efficiency (η) is calculated as follows [49]:
η = (rH2 × ΔcHH2 + rCO × ΔcHCO − rCH4 × ΔcHCH4)/Psolar irradiation
The values of ΔcHH2, ΔcHCO, and ΔcHCH4 were calculated under working temperatures. Psolar irradiation is the power of the UV-Vis-IR irradiation focused into the reactor. An optical power meter (Newport 1918-R) was used to measure the power of the UV-Vis-IR irradiation into the reactor.

3.4. Catalytic CRM Activity in the Dark and Under UV-Vis-IR Irradiation

The catalytic CRM of the sample at different temperatures in the dark or under UV-Vis-IR irradiation was assessed on the reactor equipped with quartz window. The catalyst (0.005 g) was placed into the reactor with a continuous feed stream of 10.5–10.5–79.0 vol% CH4-CO2-Ar at a rate of 40.3 mL min−1, and the electric furnace with temperature control program was used to control reaction temperature in the dark and under UV-Vis-IR irradiation.

4. Conclusions

In summary, we designed novel Co cluster-modified Ni nanoparticles on Co-Ni/SiO2 nanocomposite for light-driven thermocatalytic CRM under UV-Vis-IR irradiation. The Co-Ni/SiO2 nanocomposite displays high H2 and CO production (22.8 and 26.7 mmol min−1 g−1, respectively) and superior catalytic durability under light irradiation. Efficient photothermal conversion originates from the plasma absorption of the Ni nanoparticles, while the infrared heating effect is the origin of the high yield production. Co-Ni/SiO2 demonstrates better catalytic durability than the Ni/SiO2 catalyst that is attributed to the cluster-modification of Co, which can inhibit coke deposition on the Ni nanoparticles (active sites) in Co-Ni/SiO2. The light in the CRM reaction not only acts as a heating source but also induces photoactivation, thus further enhancing the activity by reducing the apparent activation energy of CRM. This study provides helpful insights for rationally designing Ni-based catalysts with good catalytic activity and superior catalytic durability for solar light-driven CO2 reduction, thus reducing the greenhouse effect and energy shortage.

Supplementary Materials

The following supporting information can be downloaded at https://www.mdpi.com/article/10.3390/molecules29225338/s1, Scheme S1: Structural diagram of home-made stainless steel reactor; Figure S1: Co, Ni, Si, and O HAADF-STEM mapping of Co-Ni/SiO2; Figure S2: (a) TEM and (b) HRTEM image of Ni/SiO2; Figure S3: (a) Si 2p and (b) Co 2p XPS spectra of Co-Ni/SiO2; Figure S4: N2 adsorption/desorption isotherms of (a) Co-Ni/SiO2 and (b) Ni/SiO2; Figure S5: Specific production rate of H2 and CO on Co-Ni/SiO2 for light-driven thermocatalytic CRM under focused irradiation with wavelengths above 420, 560, and 690 nm; Figure S6: TEM (a) and HRTEM (b) images for used Co-Ni/SiO2, and TEM (c) and HRTEM (d) images for used Ni/SiO2 samples after light-driven thermocatalytic durability tests; Figure S7: Stable temperature (Tst) of the Co-Ni/SiO2 under visible-infrared and infrared irradiation with wavelengths above 420, 560, and 690 nm.

Author Contributions

M.L.: Writing—original draft. Y.Z.: Writing—original draft. Data curation N.S.: Data curation, Funding acquisition. D.C.: Formal analysis. P.S.: Writing—review and editing. Q.Z.: Validation, Methodology, Project administration, Conceptualization. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the Natural Science Foundation of Shandong Province (grant numbers ZR2021QC089, ZR2021QE276, and ZR2021QB189), the National Natural Science Foundation of China (grant number 22102118), and the Project of Medical and Health Science and Technology Development Plan of Shandong Province (grant number 202213050624). We also thank Jilin Bai (State Key Laboratory of Silicate Materials for Architectures) for the XPS analysis at Wuhan University of Technology.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Informed consent was obtained from all subjects involved in the study.

Data Availability Statement

Data are contained within the article and Supplementary Materials; further inquiries can be directed to the corresponding author.

Conflicts of Interest

The authors declare no conflicts of interest.

References

  1. Xu, X.; Ray, R.; Gu, Y.; Ploehn, H.J.; Gearheart, L.; Raker, K.; Scrivens, W.A. Electrophoretic analysis and purification of fluorescent single-walled carbon nanotube fragments. J. Am. Chem. Soc. 2004, 126, 12736–12747. [Google Scholar] [CrossRef]
  2. Li, D.D.; Kassymove, M.; Cai, X.C.; Zang, S.Q.; Jiang, H.L. Photocatalytic CO2 reduction over metal-organic framework-based materials. Coord. Chem. Rev. 2020, 412, 213262–213278. [Google Scholar] [CrossRef]
  3. Wang, Y.Y.; Qu, Y.; Qu, B.H.; Bai, L.L.; Liu, Y.; Yang, Z.D.; Zhang, W.; Jing, L.Q.; Fu, H.G. Construction of six-oxygen-coordinated single Ni sites on g-C3N4 with boron-oxo species for photocatalytic water-activation-induced CO2 reduction. Adv. Mater. 2021, 33, 2105482. [Google Scholar] [CrossRef]
  4. Gong, E.; Ali, S.; Hiragond, C.B.; Kim, H.S.; Powar, N.S.; Kim, D.Y.; Kim, H.; Ln, S.I. Solar fuels: Research and development strategies to accelerate photocatalytic CO2 conversion into hydrocarbon fuels. Energy Environ. Sci. 2022, 15, 880–937. [Google Scholar] [CrossRef]
  5. Cheng, L.; Yue, X.Y.; Fan, J.J.; Xiang, Q.J. Site-specific Electron-driving observations of CO2-to-CH4 photoreduction on Co-doped CeO2/crystalline carbon nitride S-scheme heterojunctions. Adv. Mater. 2022, 34, 2200929. [Google Scholar] [CrossRef]
  6. Bian, J.; Zhang, Z.Q.; Feng, J.N.; Thangamuthu, M.; Yang, F.; Sun, L.; Li, Z.J.; Qu, Y.; Tang, D.Y.; Lin, Z.W.; et al. Energy platform for directed charge transfer in the cascade Z-scheme heterojunction: CO2 photoreduction without a cocatalyst. Angew. Chem. Int. Ed. 2021, 133, 21074–21082. [Google Scholar] [CrossRef]
  7. Zhao, L.N.; Bian, J.; Zhang, X.F.; Bai, L.L.; Xu, L.Y.; Qu, Y.; Li, Z.J.; Li, Y.X.; Jing, L.Q. Construction of ultrathin S-scheme heterojunctions of single Ni atom immobilized Ti-MOF and BiVO4 for CO2 photoconversion of nearly 100% to CO by pure water. Adv. Mater. 2022, 34, 2205303. [Google Scholar] [CrossRef]
  8. Han, K.; Wang, Y.; Wang, S.; Liu, Q.; Deng, Z.; Wang, F. Narrowing band gap energy of CeO2 in (Ni/CeO2)@SiO2 catalyst for photothermal methane dry reforming. Chem. Eng. J. 2021, 421, 129989. [Google Scholar] [CrossRef]
  9. Zhao, J.; Guo, X.; Shi, R.; Waterhouse, G.I.N.; Zhang, X.; Dai, Q.; Zhang, T. NiFe nanoalloys derived from layered double hydroxides for photothermal synergistic reforming of CH4 with CO2. Adv. Funct. Mater. 2022, 32, 2204056. [Google Scholar] [CrossRef]
  10. Zhang, Z.Y.; Zhang, T.; Liang, W.P.; Bai, P.W.; Zheng, H.Y.; Lei, Y.; Hu, Z.; Xie, T. Promoted solar-driven dry reforming of methane with Pt/mesoporous-TiO2 photo-thermal synergistic catalyst: Performance and mechanism study. Energy Convers. Manag. 2022, 58, 115496. [Google Scholar] [CrossRef]
  11. Pan, F.P.; Xiang, X.M.; Du, Z.C.; Sarnello, E.; Li, T.; Li, Y. Integrating photocatalysis and thermocatalysis to enable efficient CO2 reforming of methane on Pt supported CeO2 with Zn doping and atomic layer deposited MgO overcoating. Appl. Catal. B 2020, 260, 118189. [Google Scholar] [CrossRef]
  12. Feng, X.H.; Du, Z.C.; Sarnello, E.; Deng, W.; Petru, C.R.; Fang, L.Z.; Li, T.; Li, Y. Syngas production at a near-unity H2/CO ratio from photo-thermo-chemical dry reforming of methane on a Pt decorated Al2O3–CeO2 catalyst. J. Mater. Chem. A 2022, 10, 7896–7910. [Google Scholar] [CrossRef]
  13. Liu, H.; Meng, X.; Dao, T.D.; Zhang, H.; Li, P.; Chang, K.; Wang, T.; Li, M.; Nagao, T.; Ye, J. Conversion of carbon dioxide by methane reforming under visible-light irradiation: Surface-plasmon-mediated nonpolar molecule activation. Angew. Chem. Int. Ed. 2015, 127, 11707–11711. [Google Scholar] [CrossRef]
  14. Liu, H.M.; Li, M.; Dao, T.D.; Liu, Y.Y.; Zhou, W.; Liu, L.Q.; Meng, X.G.; Nagao, T.; Ye, J.H. Design of PdAu alloy plasmonic nanoparticles for improved catalytic performance in CO2 reduction with visible light irradiation. Nano Energy 2016, 26, 398–404. [Google Scholar] [CrossRef]
  15. Han, B.; Wei, W.; Chang, L.; Cheng, P.F.; Hu, Y.H. Efficient visible light photocatalytic CO2 reforming of CH4. ACS Catal. 2016, 6, 494–497. [Google Scholar] [CrossRef]
  16. Yang, Y.; Chai, Z.; Qin, X.; Zhang, Z.; Muhetaer, A.; Wang, C.; Huang, H.; Yang, C.; Ma, D.; Li, Q.; et al. Light-induced redox looping of a rhodium/CexWO3 photocatalyst for highly active and robust dry reforming of methane. Angew. Chem. Int. Ed. 2021, 61, e202200567. [Google Scholar] [CrossRef]
  17. Mao, M.Y.; Zhang, Q.; Yang, Y.; Li, Y.Z.; Huang, H.; Jiang, Z.K.; Hu, Q.Q.; Zhao, X.J. Solar-light-driven CO2 reduction by methane on Pt nanocrystals partially embedded in mesoporous CeO2 nanorods with high light-to-fuel efficiency. Green. Chem. 2018, 20, 2857–2869. [Google Scholar] [CrossRef]
  18. Zhang, Q.; Mao, M.Y.; Li, Y.Z.; Yang, Y.; Huang, H.; Jiang, Z.K.; Hu, Q.Q.; Wu, S.W.; Zhao, X.J. Novel photoactivation promoted light-driven CO2 reduction by CH4 on Ni/CeO2 nanocomposite with high light-to-fuel efficiency and enhanced stability. Appl. Catal. B 2018, 239, 555–564. [Google Scholar] [CrossRef]
  19. Zhang, G.Q.; Wu, S.W.; Li, Y.Z.; Zhang, Q. Significant improvement in activity; durability; and light-to-fuel efficiency of Ni nanoparticles by La2O3 cluster modification for photothermocatalytic CO2 reduction. Appl. Catal. B 2020, 264, 118544. [Google Scholar] [CrossRef]
  20. Ling, L.L.; Yang, W.J.; Yan, P.; Wang, M.; Jiang, H.L. Light-assisted CO2 hydrogenation over Pd3Cu@UiO-66 promoted by active sites in Close Proximity. Angew. Chem. Int. Ed. 2022, 61, e202116396. [Google Scholar] [CrossRef]
  21. Deng, B.W.; Song, H.; Peng, K.; Li, Q.; Ye, J.H. Metal-organic framework-derived Ga-Cu/CeO2 catalyst for highly efficient photothermal catalytic CO2 reduction. Appl. Catal. B 2021, 298, 120519. [Google Scholar] [CrossRef]
  22. Cui, J.X.; Wang, L.J.; Feng, L.; Meng, B.; Zhou, Z.Y.; Su, Z.M.; Wang, K.; Liu, S.M. A metal-free covalent organic framework as a photocatalyst for CO2 reduction at low CO2 concentration in a gas–solid system. J. Mater. Chem. A 2021, 9, 24895–24902. [Google Scholar] [CrossRef]
  23. Yan, J.Y.; Wang, C.H.; Ma, H.; Li, Y.Y.; Dr Liu, Y.C.; Suzuki, N.; Terashima, C.; Fujishima, A.; Zhang, X.T. Photothermal synergic enhancement of direct Z-scheme behavior of Bi4TaO8Cl/W18O49 heterostructure for CO2 reduction. Appl. Catal. B 2020, 268, 118401. [Google Scholar] [CrossRef]
  24. Zhang, L.; Meng, Y.P.; Tian, J.S.; Zhang, L.J.; Wan, S.L.; Lin, J.D.; Wang, Y. Direct coupling of thermos-and photocatalysis for conversion of CO2–H2O into fuels. ChemSusChem 2017, 10, 4709–4714. [Google Scholar] [CrossRef]
  25. Miao, C.; Chen, S.M.; Shang, K.X.; Liang, L.X.; Ouyang, J. Highly active Ni–Ru bimetallic catalyst integrated with MFI zeolite-loaded cerium zirconium oxide for dry reforming of methane. ACS Appl. Mater. Interfaces 2022, 14, 47616–47632. [Google Scholar] [CrossRef]
  26. Wang, Z.Q.; Yang, Z.Q.; Kadirova, Z.C.; Guo, M.N.; Fang, R.M.; He, J.; Yan, Y.F.; Ran, J.Y. Photothermal functional material and structure for photothermal catalytic CO2 reduction: Recent advance; application and prospect. Coord. Chem. Rev. 2022, 473, 214794. [Google Scholar] [CrossRef]
  27. Song, C.; Wang, Z.H.; Yin, Z.; Xiao, D.Q.; Ma, D. Principles and applications of photothermal catalysis. Chem. Catal. 2022, 2, 52–83. [Google Scholar] [CrossRef]
  28. Song, Y.; Ozdemir, E.; Ramesh, S.; Adishev, A.; Subramanian, S.; Harale, A.; Albuali, M.; Fadhel, B.A.; Jamal, A.; Moon, D.; et al. Dry reforming of methane by stable Ni–Mo nanocatalysts on single-crystalline MgO. Science 2020, 367, 777–781. [Google Scholar] [CrossRef]
  29. Xiao, Y.; Xie, K. Active exsolved metal–oxide interfaces in porous single-crystalline ceria monoliths for efficient and durable CH4/CO2 reforming. Angew. Chem. Int. Ed. 2022, 61, e202113079. [Google Scholar] [CrossRef]
  30. Min, H.K.; Kweon, S.; Kim, Y.W.; An, H.; Jo, D.; Park, E.D.; Shin, C.H.; Park, M.B. Atomically dispersed nickel species in a two-dimensional molecular sieve: Origin of high activity and stability in dry reforming of methane. Appl. Catal. B 2021, 298, 120627. [Google Scholar] [CrossRef]
  31. Wang, Q.Q.; Wang, W.; Cao, M.; Li, S.; Wang, P.; He, J.; Li, R.; Yan, X. Effect of interstitial carbon atoms in core-shell Ni3ZnC0.7/Al2O3 catalyst for high-performance dry reforming of methane. Appl. Catal. B 2022, 317, 121806. [Google Scholar] [CrossRef]
  32. Sun, N.N.; Wen, X.; Wang, F.; Wei, W.; Sun, Y.H. Effect of pore structure on Ni catalyst for CO2 reforming of CH4. Energy Environ. Sci. 2010, 3, 366–369. [Google Scholar] [CrossRef]
  33. Zhou, R.; Mohamedali, M.; Ren, Y.; Lu, Q.; Mahinpey, N. Facile synthesis of multi-layered nanostructured Ni/CeO2 catalyst plus in-situ pre-treatment for efficient dry reforming of methane. Appl. Catal. B 2022, 316, 121696. [Google Scholar] [CrossRef]
  34. Pan, Y.X.; Kuai, P.; Liu, Y.; Ge, Q.; Liu, C.J. Promotion effects of Ga2O3 on CO2 adsorption and conversion over a SiO2-supported Ni catalyst. Energy Environ. Sci. 2010, 3, 1322–1325. [Google Scholar] [CrossRef]
  35. Miao, C.; Shang, K.X.; Liang, L.X.; Chen, S.M.; Ouyang, J. A superior strategy for CO2 methanation under atmospheric pressure: Organic acid-assisted Co nanoparticles assembly on diatomite. Fuel 2023, 351, 128931. [Google Scholar]
  36. Lu, Y.; Kang, L.; Guo, D.; Zhao, Y.; Zhao, Y.; Wang, S.; Ma, X. Double-site doping of a V promoter on NixV-MgAl catalysts for the DRM reaction: Simultaneous effect on CH4 and CO2 activation. ACS Catal. 2021, 11, 8749–8765. [Google Scholar] [CrossRef]
  37. Wu, S.W.; Li, Y.Z.; Zhang, Q.; Hu, Q.Q.; Wu, J.C.; Zhou, C.Y.; Zhao, X.J. Formation of NiCo alloy nanoparticles on Co doped Al2O3 leads to high fuel production rate; large light-to-fuel efficiency; and excellent durability for photothermocatalytic CO2 reduction. Adv. Energy Mater. 2020, 10, 2002602. [Google Scholar] [CrossRef]
  38. Tan, X.; Wu, S.W.; Li, Y.Z.; Zhang, Q.; Hu, Q.Q.; Wu, J.C.; Zhang, A.; Zhang, Y.D. Highly efficient photothermocatalytic CO2 reduction in Ni/Mg-doped Al2O3 with high fuel production rate; largelight-to-fuel efficiency; and dood durability. Energy Environ. Mater. 2022, 5, 582–591. [Google Scholar] [CrossRef]
  39. Zhou, W.; Wang, B.H.; Tang, L.; Chen, L.; Guo, J.K.; Pan, J.B.; Lei, B.; Hu, B.; Bai, Z.J.; Tulu, M.; et al. Photocatalytic dry reforming of methane enhanced by “dual-path” strategy with excellent low-temperature catalytic performance. Adv. Funct. Mater. 2023, 33, 2214068. [Google Scholar] [CrossRef]
  40. Pan, F.P.; Xiang, X.M.; Deng, W.; Zhao, H.L.; Feng, X.H.; Li, Y. A novel photo-thermochemical approach for enhanced carbon dioxide reforming of methane. ChemCatChem 2018, 10, 940–945. [Google Scholar] [CrossRef]
  41. Kim, S.M.; Abdala, P.M.; Margossian, T.; Hosseini, D.; Foppa, L.; Armutlulu, A.; Beek, W.V.; Orcid, A.C.V.; Copéret, C.; Müller, C. Cooperativity and dynamics increase the performance of NiFe dry reforming catalysts. J. Am. Chem. Soc. 2017, 139, 1937–1949. [Google Scholar] [CrossRef] [PubMed]
  42. Wu, S.W.; Hu, Q.Q.; Li, Y.Z. Photothermocatalytic CO2 reduction on magnesium oxide-cluster-modified Ni nanoparticles with high fuel production rate; large light-to-fuel efficiency and excellent durability. Sol. RRL 2021, 5, 202100735. [Google Scholar] [CrossRef]
  43. Jiang, Z.K.; Li, Y.Z.; Zhang, Q.; Yang, Y.; Wu, S.W. A novel nanocomposite of mesoporous silica supported Ni nanocrystals modified by ceria clusters with extremely high light-to-fuel efficiency for UV-vis-IR light-driven CO2 reduction. J. Mater. Chem. A 2019, 7, 4881–4892. [Google Scholar] [CrossRef]
  44. Zhang, Q.; Li, Y.Z.; Wu, S.W.; Wu, J.C.; Jiang, Z.K.; Yang, Y.; Ren, L.; Zhao, X.J. UV-vis-IR irradiation driven CO2 reduction with high light-to-fuel efficiency on a unique nanocomposite of Ni nanoparticles loaded on Ni doped Al2O3 nanosheets. J. Mater. Chem. A 2019, 7, 19800–19810. [Google Scholar] [CrossRef]
  45. Khan, I.S.; Mateo, D.; Shterk, G.; Shoinkhorova, T.; Poloneeva, D.; Garzón-Tovar, L.; Gascon, J. An efficient metal-organic framework-derived nickel catalyst for the light driven methanation of CO2. Angew. Chem. 2021, 133, 26680–26686. [Google Scholar] [CrossRef]
  46. Cai, M.; Wu, Z.; Li, Z.; Wang, L.; Sun, W.; Tountas, A.A.; Li, C.; Wang, S.H.; Feng, K.; Xu, A.B.; et al. Greenhouse-inspired supra-photothermal CO2 catalysis. Nat. Energy 2021, 6, 807–814. [Google Scholar] [CrossRef]
  47. Ren, Y.Q.; Fu, Y.W.; Li, N.X.; You, C.J.; Huang, J.; Huang, K.; Sun, Z.K.; Zhou, J.C.; Si, Y.T.; Zhu, Y.H.; et al. Concentrated solar CO2 reduction in H2O vapour with >1% energy conversion efficiency. Nat. Commun. 2024, 15, 4675. [Google Scholar] [CrossRef]
  48. Huang, H.; Mao, M.Y.; Zhang, Q.; Li, Y.Z.; Bai, J.L.; Yang, Y.; Zeng, M.; Zhao, X.J. Solar-light-driven CO2 reduction by CH4 on silica-cluster-modified Ni nanocrystals with a high solar-to-fuel efficiency and excellent durability. Adv. Energy Mater. 2018, 8, 1702472. [Google Scholar] [CrossRef]
  49. Wagner, C.D.; Riggs, W.M.; Davis, L.E. Handbook of X-Ray Photoelectron Spectroscopy; Perkin-Elmer: Waltham, MA, USA, 1979. [Google Scholar]
Molecules 29 05338 g001
Figure 1. (a) XRD pattern, (b,c) TEM and HRTEM image, (d) XPS spectra of Ni 2p3/2, and (e,f) HAADF-STEM image of Co-Ni/SiO2.
Figure 1. (a) XRD pattern, (b,c) TEM and HRTEM image, (d) XPS spectra of Ni 2p3/2, and (e,f) HAADF-STEM image of Co-Ni/SiO2.
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Molecules 29 05338 g002
Figure 2. (a) The specific reaction rate of CH4 and CO2, (b) the specific production rate of H2 and CO, (c) the light-to-fuel efficiency for light-driven thermocatalytic CRM under focused UV-Vis-IR irradiation, and (d) the light-to-fuel efficiency for the light-driven thermocatalytic CRM of Co-Ni/SiO2 under the vis-IR light or infrared light from the Xe lamp.
Figure 2. (a) The specific reaction rate of CH4 and CO2, (b) the specific production rate of H2 and CO, (c) the light-to-fuel efficiency for light-driven thermocatalytic CRM under focused UV-Vis-IR irradiation, and (d) the light-to-fuel efficiency for the light-driven thermocatalytic CRM of Co-Ni/SiO2 under the vis-IR light or infrared light from the Xe lamp.
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Molecules 29 05338 g003
Figure 3. (a) The time course of the reaction and production rates for Co-Ni/SiO2 with focused UV-Vis-IR irradiation and in the dark. (b) The time course of the reaction and production rates for Ni/SiO2 with focused UV-Vis-IR irradiation, TG-MS profiles for the used Co-Ni/SiO2 (c) and Ni/SiO2 (d) samples after the durability tests.
Figure 3. (a) The time course of the reaction and production rates for Co-Ni/SiO2 with focused UV-Vis-IR irradiation and in the dark. (b) The time course of the reaction and production rates for Ni/SiO2 with focused UV-Vis-IR irradiation, TG-MS profiles for the used Co-Ni/SiO2 (c) and Ni/SiO2 (d) samples after the durability tests.
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Molecules 29 05338 g004
Figure 4. (a) The diffuse reflectance UV-vis-infrared absorption spectra of the samples. (b) The time course of H2 and CO production rates of the Co-Ni/SiO2 sample for CRM under focused UV-Vis-IR irradiation at near-room temperature. (c) The stable temperature (Tst) of Co-Ni/SiO2, Ni/SiO2, and the sample holder under focused UV-Vis-IR irradiation.
Figure 4. (a) The diffuse reflectance UV-vis-infrared absorption spectra of the samples. (b) The time course of H2 and CO production rates of the Co-Ni/SiO2 sample for CRM under focused UV-Vis-IR irradiation at near-room temperature. (c) The stable temperature (Tst) of Co-Ni/SiO2, Ni/SiO2, and the sample holder under focused UV-Vis-IR irradiation.
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Molecules 29 05338 g005
Figure 5. The rCH4 and rCO2 of the Co-Ni/SiO2 sample for CRM at different temperatures under focused UV-Vis-IR and in the dark (a,b), and ln(rCO2) vs. 1/T (C) for CRM on Co-Ni/SiO2 under focused irradiation and in the dark (c).
Figure 5. The rCH4 and rCO2 of the Co-Ni/SiO2 sample for CRM at different temperatures under focused UV-Vis-IR and in the dark (a,b), and ln(rCO2) vs. 1/T (C) for CRM on Co-Ni/SiO2 under focused irradiation and in the dark (c).
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Li, M.; Zhang, Y.; Sun, N.; Cheng, D.; Sun, P.; Zhang, Q. Co Cluster-Modified Ni Nanoparticles with Superior Light-Driven Thermocatalytic CO2 Reduction by CH4. Molecules 2024, 29, 5338. https://doi.org/10.3390/molecules29225338

AMA Style

Li M, Zhang Y, Sun N, Cheng D, Sun P, Zhang Q. Co Cluster-Modified Ni Nanoparticles with Superior Light-Driven Thermocatalytic CO2 Reduction by CH4. Molecules. 2024; 29(22):5338. https://doi.org/10.3390/molecules29225338

Chicago/Turabian Style

Li, Mei, Yuhua Zhang, Na Sun, Dan Cheng, Peng Sun, and Qian Zhang. 2024. "Co Cluster-Modified Ni Nanoparticles with Superior Light-Driven Thermocatalytic CO2 Reduction by CH4" Molecules 29, no. 22: 5338. https://doi.org/10.3390/molecules29225338

APA Style

Li, M., Zhang, Y., Sun, N., Cheng, D., Sun, P., & Zhang, Q. (2024). Co Cluster-Modified Ni Nanoparticles with Superior Light-Driven Thermocatalytic CO2 Reduction by CH4. Molecules, 29(22), 5338. https://doi.org/10.3390/molecules29225338

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