Construction of Ru Single-Atoms on Ceria to Reform the Products of CO<sub>2</sub> Photoreduction

Li, Xiaoyao; Wang, Min; Wang, Rongyan; Wang, Yang; Zhu, Min; Zhang, Lingxia; Shi, Jianlin

doi:10.1021/acsnano.3c12001

Cited by 3 publications

(1 citation statement)

References 40 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As a result, the CC bond was weakened and then elongated from an initial bond length of 1.205 to 1.247 Å. These results indicate that the C 2 H 2 molecule has been effectively activated by Ni atoms and no longer maintains the original linear configuration . The longer bond length obtained from Ni–Ru/C in comparison with other structures indicates that the CC bond was maximally weakened, leading to the preferential activation of C 2 H 2 during the catalytic process.…”

Section: Resultsmentioning

confidence: 99%

Lattice-Strain Engineering in Ni–Ru Heterostructures for Efficient Acetylene Hydrochlorination toward Vinyl Chloride

Fan,

Wang,

Liu

et al. 2024

ACS Nano

View full text Add to dashboard Cite

Ru-based catalysts have emerged as promising alternatives to HgCl 2 in vinyl chloride monomer (VCM) production by acetylene hydrochlorination. However, poor C 2 H 2 activation and the generation of key intermediates (*CH 2 �CH) have posed grand challenges for enhanced catalytic performances. Herein, we synthesized a Ni-intercalated Ru heterostructure using a lattice-strain engineering strategy, resulting in the desired electronic and chemical environments. The collaboration of Ni splits the adsorption centers of C 2 H 2 and HCl by weakening the strong steric hindrance, and it also promotes the activation of the linear C�C configurations. The well-controlled lattice strain enables strong d−d hybridization interactions between Ni and Ru, resulting in an upshift of the d-band center from −3.72 eV (for Ru/C) to −3.49 eV and electronic delocalization. This optimized local Ni−Ru/C structure thus enhances *H adsorption while weakening the energy barrier for generating *CH 2 �CH intermediates. Furthermore, the energy barrier for VCM formation was simultaneously reduced. Accordingly, the Ni−Ru/C heterostructures achieve improved performance in pilot-scale trials, with a conversion of >99.2% and stability for over 500 h. These performances significantly surpass most reported Ru-based moieties and the traditional Hg catalysts, offering a promising avenue for C 2 H 2 activation in industrial applications.

show abstract

Section: Resultsmentioning

confidence: 99%

Lattice-Strain Engineering in Ni–Ru Heterostructures for Efficient Acetylene Hydrochlorination toward Vinyl Chloride

Fan,

Wang,

Liu

et al. 2024

ACS Nano

View full text Add to dashboard Cite

show abstract

AuAg plasmonic nanoalloys with asymmetric charge distribution on CeO₂ nanorods for selective photocatalytic CO₂‐to‐CH₄ conversion

Yan,

Xu,

Jin

et al. 2024

cMat

View full text Add to dashboard Cite

Converting CO2 under mild conditions by employing semiconductor photocatalysts is promising to address global environmental issues. However, the current CO2 conversion efficiency is limited by the difficulty activating the thermodynamically stable CO2 molecules. Constructing plasmonic nanoalloy‐based photocatalytic systems with significant localized surface plasmon resonance (LSPR) is full of potential but remains a vast challenge. In this work, AuAg plasmonic nanoalloys were incorporated on CeO2 nanorods (designated as AuAg–CeO2) to achieve selective photoreduction of CO2. The result displays that Ag can serve as a superior electron modifier to promote the electron enrichment of Au, thus producing asymmetric charge distributions to boost the selective conversion of CO2. Furthermore, the improved LSPR effect on AuAg–CeO2 induces the generation of high‐energy hot electrons under irradiation, enhancing the reactivity of electrons for CO2 photoreduction. Due to the aforementioned effects, AuAg–CeO2 exhibits a high CO2‐to‐CH4 performance of 92.6 μmol g−1 through a 3‐h test and a high CH4 selectivity of 94.5%, up to 2.6, 8.7, and 17.1 times higher than the activity of Au–CeO2, pure CeO2, and Ag–CeO2, respectively. This work can provide a new perspective for constructing high‐performance catalysts for photocatalytic CO2 reduction.

show abstract

Concerted Proton-Coupled Electron Transfer by Mo⁵⁺/Mo⁶⁺ Reversible Transformation for CO₂ Photoreduction with Nearly 100% CH₄ Selectivity

Liang,

Fan,

Ding

et al. 2024

ACS Catal.

View full text Add to dashboard Cite

Regulation of the proton-coupled electron transfer (PCET) process to avoid the unbalanced proton and electron regions on the reduction active sites is key to dictating product selectivity in a photocatalytic CO 2 reduction reaction. Here, we show that reversible Mo 5+ /Mo 6+ as a mediator can regulate the proton and electron transfer process at the Bi 2 MoO 6 nanosheet/In 2 O 3 microtube (BI) catalyst. The formed concerted proton-coupled electron transfer enables a champion solar-to-methane efficiency of 0.15%, resulting in nearly 100% CH 4 selectivity and a competitive CH 4 yield of 46.37 μmol g −1 h −1 in pure water. The experiments, together with theoretical calculations, clearly validate that In sites as H 2 O oxidation centers provide protons, and the regulation of protons and electrons by using Mo sites forms approximate electroneutral proton/ electron pairs, which are conjointly transferred to Bi sites as CO 2 adsorption/reduction centers, thus achieving precise hydrogenation on Bi sites for binding of the *CH 3 O key intermediate to form CH 4 .

show abstract

Construction of Ru Single-Atoms on Ceria to Reform the Products of CO₂ Photoreduction

Cited by 3 publications

References 40 publications

Lattice-Strain Engineering in Ni–Ru Heterostructures for Efficient Acetylene Hydrochlorination toward Vinyl Chloride

Lattice-Strain Engineering in Ni–Ru Heterostructures for Efficient Acetylene Hydrochlorination toward Vinyl Chloride

AuAg plasmonic nanoalloys with asymmetric charge distribution on CeO₂ nanorods for selective photocatalytic CO₂‐to‐CH₄ conversion

Concerted Proton-Coupled Electron Transfer by Mo⁵⁺/Mo⁶⁺ Reversible Transformation for CO₂ Photoreduction with Nearly 100% CH₄ Selectivity

Contact Info

Product

Resources

About

Construction of Ru Single-Atoms on Ceria to Reform the Products of CO2 Photoreduction

Cited by 3 publications

References 40 publications

Lattice-Strain Engineering in Ni–Ru Heterostructures for Efficient Acetylene Hydrochlorination toward Vinyl Chloride

Lattice-Strain Engineering in Ni–Ru Heterostructures for Efficient Acetylene Hydrochlorination toward Vinyl Chloride

AuAg plasmonic nanoalloys with asymmetric charge distribution on CeO2 nanorods for selective photocatalytic CO2‐to‐CH4 conversion

Concerted Proton-Coupled Electron Transfer by Mo5+/Mo6+ Reversible Transformation for CO2 Photoreduction with Nearly 100% CH4 Selectivity

Contact Info

Product

Resources

About

Construction of Ru Single-Atoms on Ceria to Reform the Products of CO₂ Photoreduction

AuAg plasmonic nanoalloys with asymmetric charge distribution on CeO₂ nanorods for selective photocatalytic CO₂‐to‐CH₄ conversion

Concerted Proton-Coupled Electron Transfer by Mo⁵⁺/Mo⁶⁺ Reversible Transformation for CO₂ Photoreduction with Nearly 100% CH₄ Selectivity