Carbon with Surface‐Enriched Nitrogen and Sulfur Supported Au Catalysts for Acetylene Hydrochlorination

Wang, Bolin; Zhao, Jia; Yue, Yuxue; Sheng, Gangfeng; Lai, Huixia; Rui, Jiayao; He, Huiwen; Hu, Zhong‐Ting; Feng, Feng; Zhang, Qunfeng; Guo, Lingling; Li, Xiaonian

doi:10.1002/cctc.201801555

Cited by 34 publications

(11 citation statements)

References 53 publications

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“…To clarify the interaction between N‐containing functional groups and CuNi species in this work, the XPS fine spectra in N 1s region has been also scanned (Figure 6D). The N 1s high‐resolution spectrum of rss AC revealed that there were three peaks located at 398.4, 400.1, 407.5 eV corresponding to the pyridinic‐N, pyrrolic‐N and oxidized‐N [45] . The corresponding peaks of CuNi/ rss AC have been centered at 399.0, 400.8 and 407.5 eV.…”

Section: Resultsmentioning

confidence: 98%

Construction of Dot‐Matrix Cu⁰‐Cu₁Ni₃ Alloy Nano‐Dispersions on the Surface of Porous N‐Autodoped Biochar for Selective Hydrogenation of Furfural

Yang

Ning

et al. 2021

ChemCatChem

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Using cheap Cu‐based catalysts for highly selective hydrogenation of furfural (FAL) is of great importance of upgrading this biomass‐derived platform molecule but is still challenging for large‐scale application due to the low conversion efficiency and the easy aggregation of Cu active sites. To address these issues, a nitrogen‐autodoped porous biochar derived from rubber seed shell (rssAC) was fabricated for anchoring Cu sites on a nanoscale. Moreover, by the co‐crystallization strategy of Cu and the second metal (M, M=Ni, Zn, Co, Ce), stable Cu−M nanoalloys were constructed on the surface of the rssAC support. The FAL hydrogenation experiments showed that the type, proportion and loading amount of the second metal had great effect on the catalytic efficiency. Compared with the other metals, Ni‐doped Cu/rssAC catalyst exhibited the best hydrogenation performance due to their extraordinary adsorption and activation capacity for hydrogen. Further, the highest catalytic efficiency was observed using 20 % Cu1Ni1/rssAC catalyst. The characterization results showed that the key to its success was highly‐dispersive anchoring of the CuNi active sites onto the inner/outer surface of the nanopores of rssAC support by the strong interaction between the surface N‐containing functional groups and metals. Of note, the formed CuNi alloys with the Cu/Ni atomic ratio of 1 : 3 played an important role in the stabilization of the adjacent nano‐dot matrix Cu0 species. Kinetic test indicated that the formation step of furfuryl alcohol (FOL) from FAL was still the key step and the hydrogenation products can be converted between FOL and tetrahydrofurfuryl alcohol (THFA). The life evaluation test showed that the catalyst still kept high activity and selectivity after being reused five times. The advanced synthesis method co‐using N‐doped support anchoring and the second metal alloying strategy sheds light on preparing effective catalysts for hydrogenation of biomass‐based compounds.

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Section: Resultsmentioning

confidence: 98%

Construction of Dot‐Matrix Cu⁰‐Cu₁Ni₃ Alloy Nano‐Dispersions on the Surface of Porous N‐Autodoped Biochar for Selective Hydrogenation of Furfural

Yang

Ning

et al. 2021

ChemCatChem

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“…Recently, single atomically dispersed catalysts (also called single-atom catalysts, SACs) have emerged as a cutting-edge field in heterogeneous catalysis, not only due to their 100% atomic utilization efficiency but also due to their outstanding catalytic performance in water splitting, oxygen reduction, acetylene hydrochlorination, − and other heterogeneous catalytic reactions. , Generally, the strong interaction between ligands and metals plays a key role in segregating, dispersing, and stabilizing single metal-atoms and further affects the catalytic behavior of metal-sites. − Currently, the structures of metals, including coordination environment, binding modes, and oxidation state regulation induced by the defects or/and functions on the supports, remain a great challenge to the synthesis and regulation of SACs. Meanwhile, very few studies − have been performed to unveil the catalytic features and mechanisms on vacancy-defect sites, suggesting the necessity to determine how these sites with different structures catalyze the reaction.…”

Section: Introductionmentioning

confidence: 99%

Controllable Synthesis of Vacancy-Defect Cu Site and Its Catalysis for the Manufacture of Vinyl Chloride Monomer

et al. 2021

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Designing favorable structures of active sites and clarifying the structure− activity relationship are important to narrow the large activity gap between Cu-based and the noble-metal-based catalytic systems for vinyl chloride production. Herein, we report a facile controllable thermal method for fabricating the platform of Cu single-atom catalysts ranging from the standard no-vacancy-defect CuCl 3 −N to vacancy-defect CuCl 2 V−N ("V" for the vacancy-defect site) and to no-vacancy-defect CuN 4 . The gradually released C−Cl derivatives promote the vacancy-defect generation under elevated temperatures, and the activity gap between Cu-and the noble-metal-based systems is found to be dramatically narrowed from classic ∼37-fold to ∼1.5-fold on the vacancy-defect sites. Kinetic analysis shows that the competitive adsorption between acetylene and hydrogen chloride on the CuCl 2 V−N site contributed more to the catalytic performance than the single hydrogen chloride adsorption on site CuCl 3 −N or CuN 4 . Furthermore, when the CuCl 2 V−N site is preoccupied and adsorbed by acetylene, the reaction energy barrier decreases from 35 to 24 kJ/mol, indicating that the single activation of acetylene is more favorable for catalytic activity than that of the dualactivation of acetylene and hydrogen chloride. DFT calculations revealed the specific reaction mechanism catalyzed on the vacancydefect CuCl 2 V−N site, i.e., where the vacancy-defect not only affects the activation behavior of substrates but also regulates the reaction pathway. Excellent catalytic performance can be maintained under the interaction of high concentration of vinyl chloride and H 2 S impurity. This work opens a new window for controllable synthesis of vacancy-defect sites of single metallic atoms in catalysis design and enhancing catalytic activity.

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“…[ 29–31 ] Subsequently, numerous studies have been carried out to improve the stability of gold chloride by adding other additives. [ 32–42 ]…”

Section: Introductionmentioning

confidence: 99%

Constructing the single‐site of pyridine‐based organic compounds for acetylene hydrochlorination: From theory to experiment

Zhao

Xue

et al. 2021

Applied Organom Chemis

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Acetylene hydrochlorination reaction requires toxic mercuric chloride catalyst, which caused serious environmental pollution by mercury in recent years. Though Au‐based catalysts show the best catalytic activity and high rates of acetylene conversion, much work still needs to be done to reduce the cost before their large‐scale applications. Here, a pure pyridine‐based organic polymer was successfully designed and assembled, which contains only one nitrogen species and exhibits a high activity with acetylene conversion reaching 88% and the selectivity of vinyl chloride above 99%. Both experimental and density functional theory (DFT) studies directly demonstrate that the pyridinic N atom in pyridine ring is the active site of the catalyst and the insertion of acetylene to HCl might be the rate‐determining step. Different from traditional carbonization and aminating treatment at high temperature, the pyridine‐based polymers were obtained by polymerization in liquid phase. Besides, the activity of the catalyst may be determined by these combined effects of surface area, pores structure, and the amount of pyridinic N.

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Carbon with Surface‐Enriched Nitrogen and Sulfur Supported Au Catalysts for Acetylene Hydrochlorination

Cited by 34 publications

References 53 publications

Construction of Dot‐Matrix Cu⁰‐Cu₁Ni₃ Alloy Nano‐Dispersions on the Surface of Porous N‐Autodoped Biochar for Selective Hydrogenation of Furfural

Construction of Dot‐Matrix Cu⁰‐Cu₁Ni₃ Alloy Nano‐Dispersions on the Surface of Porous N‐Autodoped Biochar for Selective Hydrogenation of Furfural

Controllable Synthesis of Vacancy-Defect Cu Site and Its Catalysis for the Manufacture of Vinyl Chloride Monomer

Constructing the single‐site of pyridine‐based organic compounds for acetylene hydrochlorination: From theory to experiment

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Carbon with Surface‐Enriched Nitrogen and Sulfur Supported Au Catalysts for Acetylene Hydrochlorination

Cited by 34 publications

References 53 publications

Construction of Dot‐Matrix Cu0‐Cu1Ni3 Alloy Nano‐Dispersions on the Surface of Porous N‐Autodoped Biochar for Selective Hydrogenation of Furfural

Construction of Dot‐Matrix Cu0‐Cu1Ni3 Alloy Nano‐Dispersions on the Surface of Porous N‐Autodoped Biochar for Selective Hydrogenation of Furfural

Controllable Synthesis of Vacancy-Defect Cu Site and Its Catalysis for the Manufacture of Vinyl Chloride Monomer

Constructing the single‐site of pyridine‐based organic compounds for acetylene hydrochlorination: From theory to experiment

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Construction of Dot‐Matrix Cu⁰‐Cu₁Ni₃ Alloy Nano‐Dispersions on the Surface of Porous N‐Autodoped Biochar for Selective Hydrogenation of Furfural

Construction of Dot‐Matrix Cu⁰‐Cu₁Ni₃ Alloy Nano‐Dispersions on the Surface of Porous N‐Autodoped Biochar for Selective Hydrogenation of Furfural