Density functional theory study of mercury adsorption and oxidation on CuO(111) surface

Sun, Song; Zhang, Dongsheng; Li, Chunyu; Wang, Yanji; Yang, Qiusheng

doi:10.1016/j.cej.2014.07.081

Cited by 53 publications

(23 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[3,43] In addition, it is wellestablished that the metal atoms in metal oxides dominantly contribute to the catalytic activity of metal oxides. [42,44] Accordingly, the activity of catalytic Cu atoms governs the overall NRR activity of CuO/RGO. Here, CuO(111) surface is selected for slab modeling, because CuO(111) exhibits the lowest surface energy and is thus most stable among seven low-index surfaces ( Figure S16, Table S1), in consistence with the literature results.…”

Section: Cuo/graphene Nanocomposite For Nitrogen Reduction Reactionmentioning

confidence: 99%

CuO/Graphene Nanocomposite for Nitrogen Reduction Reaction

et al. 2019

View full text Add to dashboard Cite

Electrochemical conversion of N 2 to NH 3 offers a clean and energy-saving solution for artificial NH 3 production, but requires cost-effective, steady and highly efficient catalysts to promote N 2 reduction reaction (NRR). Herein, CuO employed as a new non-noble-metal NRR catalyst was investigated both experimentally and theoretically. When supporting the CuO nanoparticles on reduced graphene oxide (RGO), it was demonstrated that the resulting CuO/RGO nanocomposite could effectively and robustly catalyze NRR under ambient conditions. At À 0.75 V versus reversible hydrogen electrode, the CuO/RGO exhibited a high NH 3 yield of 1.8 × 10 À 10 mol s À 1 cm À 2 and Faradaic efficiency of 3.9 %, along with the excellent selectivity and high stability. Density functional theory (DFT) calculations revealed that the "Suf-end" was the most effective mode for N 2 adsorption on catalytic Cu atoms. In NRR process, the alternating associative route was the preferable pathway with *N 2 ! *NNH being the rate-determining step.Ammonia (NH 3 ) is an essential nitrogen chemical for manufacturing fertilizers, dyes, medicaments, explosives, etc. [1] Besides, NH 3 is also deemed as the next-generation liquid fuel and highefficiency energy carrier owing to its high energy density (4.32 kWh L À 1 ) and hydrogen capacity (17.6 wt%). [2] However, at present, the artificial ammonia production depends primarily on the Haber-Bosch process that operates under high pressure (150~300 bar) and high temperature (300~550°C), [1] leading to the significant energy consumption and enormous CO 2 emission. This motivates us to develop an alternative approach for sustainable and economical NH 3 synthesis under ambient conditions.Electrochemical conversion of N 2 to NH 3 at ambient conditions offers a clean and energy-saving solution for largescale NH 3 production, but requires efficient and stable electrocatalysts to accelerate the N 2 reduction reaction (NRR) rate. [1] The noble metals such as Au, [3] Ag [4] and Ru [5] are currently recognized as excellent catalysts for NRR. Nevertheless, the scarcity and high cost of noble metals greatly hinder their large-scale applications. Recent advances demonstrate the earth-abundant transition-metal sulfides, [6,7] carbides, [8,9] nitrides [10] and oxides [11] are the cost-effective alternatives towards NRR. Of these transition-metal-based catalysts, the metal oxides have attracted the most attention due to their facile preparation, favorable catalytic activity and high stability. Sun and coworkers recently reported a series of metal oxides, including Fe 3 O 4 , [12] VO 2 , [13] Cr 2 O 3 , [14] TiO 2 , [15] Nb 2 O 5 , [16] MoO 3 [17] and β-FeOOH [18] which were found to exhibit comparable or superior NRR activities to most noble metals. Nonetheless, the potentially high NRR performance of metal oxides is greatly limited by their poor conductivity, which lowers the electron-transfer efficiency unfavourable for NRR kinetic process. The most efficient way to tackle this problem is anchoring the metal oxides onto rob...

show abstract

Section: Cuo/graphene Nanocomposite For Nitrogen Reduction Reactionmentioning

confidence: 99%

CuO/Graphene Nanocomposite for Nitrogen Reduction Reaction

et al. 2019

View full text Add to dashboard Cite

show abstract

“…Three predominant oxidized mercury species, i.e., HgCl2, HgS and HgO, were chemisorbed on Mg/DOBDC, but with different adsorption strengths. Specifically, the highest BE of HgCl2 on Mg/DOBDC was -89.0 kJ/mol, which overcomes BEs of HgCl2 on most metal oxides [28,31,34,35,67]. The corresponding stable configuration is shown in Fig.…”

Section: Oxidized Mercury Species Adsorption On Mg/dobdcmentioning

confidence: 90%

Theoretical prediction the removal of mercury from flue gas by MOFs

Liu

2016

Fuel

View full text Add to dashboard Cite

Removal of mercury from flue gas has been considered as one of the hot topics in both the scientific and industrial world. Adsorption of elemental mercury (Hg 0) and oxidized mercury species (HgCl2, HgO, and HgS) on a novel metal organic framework (MOF) material, named Mg/DOBDC, with unsaturated metal centers was investigated using density functional theory (DFT) calculations. The results show that Hg 0 stably physi-sorbed on the unsaturated metal center (magnesium ion) of Mg/DOBDC with a binding energy (BE) of-27.5 kJ/mol. A direct interaction between Hg 0 and magnesium ion was revealed by the partial density of state (PDOS) analysis. HgCl2 multi-interacts with two neighboring magnesium ions simultaneously by its Cl endings and thus resulted in strong adsorption strength (-89.0 kJ/mol). The adsorption energies of HgO and HgS on the Mg/DOBDC were as high as-117.0 kJ/mol and-169.7 kJ/mol, respectively, indicating a strong chemisorption. Theoretical calculations in this study reveal that Mg/DOBDC has the potential to serve as an efficient material for removal of mercury from flue gas.

show abstract

“…Similarly, a 4-layer 3 × 3-surface CaO (001) slab was modeled to describe the CaO surface between CaO and As 2 O 3 in this study. The superficial two layers of atoms were relaxed while the rest layers were fixed [ 38 ]. The vacuum region between slabs was set to 10 Å to avoid interactions among periodic images [ 39 ].…”

Section: Methods and Modelingmentioning

confidence: 99%

Theoretical Study of As2O3 Adsorption Mechanisms on CaO surface

et al. 2019

View full text Add to dashboard Cite

Emission of hazardous trace elements, especially arsenic from fossil fuel combustion, have become a major concern. Under an oxidizing atmosphere, most of the arsenic converts to gaseous As2O3. CaO has been proven effective in capturing As2O3. In this study, the mechanisms of As2O3 adsorption on CaO surface under O2 atmosphere were investigated by density functional theory (DFT) calculation. Stable physisorption and chemisorption structures and related reaction paths are determined; arsenite (AsO33−) is proven to be the form of adsorption products. Under the O2 atmosphere, the adsorption product is arsenate (AsO43−), while tricalcium orthoarsenate (Ca3As2O8) and dicalcium pyroarsenate (Ca2As2O7) are formed according to different adsorption structures.

show abstract

Density functional theory study of mercury adsorption and oxidation on CuO(111) surface

Cited by 53 publications

References 42 publications

CuO/Graphene Nanocomposite for Nitrogen Reduction Reaction

CuO/Graphene Nanocomposite for Nitrogen Reduction Reaction

Theoretical prediction the removal of mercury from flue gas by MOFs

Theoretical Study of As2O3 Adsorption Mechanisms on CaO surface

Contact Info

Product

Resources

About