Mechanistic Understanding of Methane-to-Methanol Conversion on Graphene-Stabilized Single-Atom Iron Centers

2021 ◽  
Author(s):  
Sungil Hong ◽  
Giannis Mpourmpakis
Keyword(s):  
Value Added ◽  
Methanol Conversion ◽  
Single Atom ◽  
Grand Challenges ◽  
Mechanistic Understanding

The functionalization of methane to value-added liquid chemicals remains as one of the “grand challenges” in chemistry. In this work, we provide insights into the direct methane-to-methanol conversion mechanisms with...

scholarly journals Platinum–copper single atom alloy catalysts with high performance towards glycerol hydrogenolysis

2019 ◽  
Vol 10 (1) ◽  
Author(s):  
Xi Zhang ◽  
Guoqing Cui ◽  
Haisong Feng ◽  
Lifang Chen ◽  
Hui Wang ◽  
...  
Keyword(s):  
Active Sites ◽  
High Performance ◽  
Reaction Pathway ◽  
Theoretical Calculations ◽  
Experimental Studies ◽  
Value Added ◽  
Catalytic Performance ◽  
Single Atom ◽  
Glycerol Hydrogenolysis ◽  
Single Atom Alloy

AbstractSelective hydrogenolysis of biomass-derived glycerol to propanediol is an important reaction to produce high value-added chemicals but remains a big challenge. Herein we report a PtCu single atom alloy (SAA) catalyst with single Pt atom dispersed on Cu nanoclusters, which exhibits dramatically boosted catalytic performance (yield: 98.8%) towards glycerol hydrogenolysis to 1,2-propanediol. Remarkably, the turnover frequency reaches up to 2.6 × 103 molglycerol·molPtCu–SAA−1·h−1, which is to our knowledge the largest value among reported heterogeneous metal catalysts. Both in situ experimental studies and theoretical calculations verify interface sites of PtCu–SAA serve as intrinsic active sites, in which the single Pt atom facilitates the breakage of central C–H bond whilst the terminal C–O bond undergoes dissociation adsorption on adjacent Cu atom. This interfacial synergistic catalysis based on PtCu–SAA changes the reaction pathway with a decreased activation energy, which can be extended to other noble metal alloy systems.

Metal Single Atom Strategy Greatly Boosts Photocatalytic Methyl Activation and C–C Coupling for the Coproduction of High-Value-Added Multicarbon Compounds and Hydrogen

ACS Catalysis ◽  
2020 ◽  
Vol 10 (16) ◽  
pp. 9109-9114 ◽  
Author(s):  
Peng Zhou ◽  
Yuguang Chao ◽  
Fan Lv ◽  
Kai Wang ◽  
Weiyu Zhang ◽  
...  
Keyword(s):  
Value Added ◽  
Single Atom

Porphyrin and single atom featured reticular materials: recent advances and future perspective of solar-driven CO2 reduction

2021 ◽  
Author(s):  
Vishnu Nair Gopalakrishnan ◽  
Jorge Becerra ◽  
Edward F. Pena ◽  
Mohan Sakar ◽  
Francois Béland ◽  
...  
Keyword(s):  
Visible Light ◽  
Visible Light Irradiation ◽  
Co2 Reduction ◽  
Value Added ◽  
Light Irradiation ◽  
Single Atom ◽  
Future Perspective ◽  
Covalent Organic Frameworks ◽  
Recent Advances

Insights into the porphyrin and single-atom featured metal- and covalent-organic frameworks for photocatalytic conversion of CO2 into value-added chemical feedstocks under visible light irradiation.

scholarly journals Ammonia electrosynthesis on single-atom catalysts: Mechanistic understanding and recent progress

2021 ◽  
Vol 2 (4) ◽  
pp. 041305
Author(s):  
Panpan Li ◽  
Zhiwei Fang ◽  
Zhaoyu Jin ◽  
Guihua Yu
Keyword(s):  
Recent Progress ◽  
Single Atom ◽  
Mechanistic Understanding

Carbon nanofibers@NiSe core/sheath nanostructures as efficient electrocatalysts for integrating highly selective methanol conversion and less-energy intensive hydrogen production

2019 ◽  
Vol 7 (45) ◽  
pp. 25878-25886 ◽  
Author(s):  
Bin Zhao ◽  
Jian-Wen Liu ◽  
Ya-Ru Yin ◽  
Dan Wu ◽  
Jing-Li Luo ◽  
...  
Keyword(s):  
Energy Consumption ◽  
Hydrogen Production ◽  
Carbon Nanofibers ◽  
Value Added ◽  
Methanol Conversion

In situ synthesized carbon nanofibers@NiSe core/sheath nanostructures act as robust and stable electrocatalysts for highly selective methanol conversion to value-added formate and boosting hydrogen production with less energy consumption.

scholarly journals Lowering the C-H Bond Activation Barrier of Methane Using SAC@Cu(111): A Periodic DFT Investigations

2021 ◽  
Author(s):  
Meema Bhati ◽  
Jignesh Dhumal ◽  
Kavita Joshi
Keyword(s):  
Density Functional ◽  
Bond Activation ◽  
Activation Barrier ◽  
Bond Cleavage ◽  
Minimum Energy ◽  
Value Added ◽  
Methane Activation ◽  
Single Atom ◽  
Activation Barriers ◽  
Metal Doped

Methane has long captured the world's spotlight for being the simplest and yet one of the most notorious hydrocarbon. Exploring its potential to be converted into value added products has raised a compelling interest. In the present work, we have studied the efficiency of Single-Atom Catalysts (SACs) for methane activation employing Density Functional Theory (DFT). The Climbing Image-Nudged Elastic Bond (CI-NEB) method is used in tandem with the Improved Dimer (ID) method to determine the minimum energy pathway for the first C-H bond dissociation of methane. Our study reported that the transition-metal doped Cu(111) surfaces enhance adsorption, activate C-H bond, and reduce activation barrier for first C-H bond cleavage of methane. The results suggest Ru/Co/Rh doped Cu(111) as promising candidates for methane activation with minimal activation barrier and less endothermic reaction. For these SACs, the calculated activation barriers for first C-H bond cleavage are 0.17 eV, 0.24 eV, and 0.26 eV respectively, which is substantially lower than 1.13 eV, the activation barrier for Cu(111).

scholarly journals Electronic Band Contraction Induced Low Temperature Methane Activation on Metal Alloys

2019 ◽  
Author(s):  
Victor Fung ◽  
Guoxiang Hu ◽  
Bobby Sumpter
Keyword(s):  
Low Temperature ◽  
Transition Metals ◽  
Metal Cluster ◽  
Value Added ◽  
Metal Alloys ◽  
Single Atom ◽  
Electronic Band ◽  
Earth Abundant ◽  
Temperature Activation ◽  
Methane Chemisorption

The catalytic conversion of methane under mild conditions is an appealing approach to selectively produce value-added products from natural gas. Catalysts which can chemisorb methane can potentially overcome challenges associated with its high stability and achieve facile activation. Although transition metals can activate C-H bonds, chemisorption and low-temperature conversion remains elusive on these surfaces. The broad electronic bands of metals can only weakly interact with the methane orbitals, in contrast to specific transition metal oxide and supported metal cluster surfaces which are now recognized to form methane σ-complexes. Here, we report methane chemisorption can, remarkably, occur on metal surfaces via electronic band contraction and localization from metal alloying. From a broad screening including single atom and intermetallic alloys in various substrates, we find early transition metals as promising metal solutes for methane chemisorption as well as low-temperature activation. These findings demonstrate a combinatorial diversity of possible candidates in earth abundant metal alloys with this attractive catalytic behavior.

scholarly journals Electronic Band Contraction Induced Low Temperature Methane Activation on Metal Alloys

2019 ◽  
Author(s):  
Victor Fung ◽  
Guoxiang Hu ◽  
Bobby Sumpter
Keyword(s):  
Low Temperature ◽  
Transition Metals ◽  
Metal Cluster ◽  
Value Added ◽  
Metal Alloys ◽  
Single Atom ◽  
Electronic Band ◽  
Earth Abundant ◽  
Temperature Activation ◽  
Methane Chemisorption

The catalytic conversion of methane under mild conditions is an appealing approach to selectively produce value-added products from natural gas. Catalysts which can chemisorb methane can potentially overcome challenges associated with its high stability and achieve facile activation. Although transition metals can activate C-H bonds, chemisorption and low-temperature conversion remains elusive on these surfaces. The broad electronic bands of metals can only weakly interact with the methane orbitals, in contrast to specific transition metal oxide and supported metal cluster surfaces which are now recognized to form methane σ-complexes. Here, we report methane chemisorption can, remarkably, occur on metal surfaces via electronic band contraction and localization from metal alloying. From a broad screening including single atom and intermetallic alloys in various substrates, we find early transition metals as promising metal solutes for methane chemisorption as well as low-temperature activation. These findings demonstrate a combinatorial diversity of possible candidates in earth abundant metal alloys with this attractive catalytic behavior.

scholarly journals Regulating kinetics and thermodynamics of electrochemical nitrogen reduction with metal single-atom catalysts in a pressurized electrolyser

2020 ◽  
Vol 117 (47) ◽  
pp. 29462-29468
Author(s):  
Haiyuan Zou ◽  
Weifeng Rong ◽  
Shuting Wei ◽  
Yongfei Ji ◽  
Lele Duan
Keyword(s):  
Driving Forces ◽  
Theoretical Calculations ◽  
Formation Rate ◽  
Reaction System ◽  
Value Added ◽  
Reduction Reaction ◽  
Single Atom ◽  
Ambient Conditions ◽  
Hydrogen Electrode ◽  
Nitrogen Reduction

Using renewable electricity to synthesize ammonia from nitrogen paves a sustainable route to making value-added chemicals but yet requires further advances in electrocatalyst development and device integration. By engineering both electrocatalyst and electrolyzer to simultaneously regulate chemical kinetics and thermodynamic driving forces of the electrocatalytic nitrogen reduction reaction (ENRR), we report herein stereoconfinement-induced densely populated metal single atoms (Rh, Ru, Co) on graphdiyne (GDY) matrix (formulated as M SA/GDY) and realized a boosted ENRR activity in a pressurized reaction system. Remarkably, under the pressurized environment, the hydrogen evolution reaction of M SA/GDY was effectively suppressed and the desired ENRR activity was strongly amplificated. As a result, the pressurized ENRR activity of Rh SA/GDY at 55 atm exhibited a record-high NH3formation rate of 74.15 μg h−1⋅cm−2, a Faraday efficiency of 20.36%, and a NH3partial current of 0.35 mA cm−2at −0.20 V versus reversible hydrogen electrode, which, respectively, displayed 7.3-, 4.9-, and 9.2-fold enhancements compared with those obtained under ambient conditions. Furthermore, a time-independent ammonia yield rate using purified15N2confirmed the concrete ammonia electroproduction. Theoretical calculations reveal that the driving force for the formation of end-on N2* on Rh SA/GDY increased by 9.62 kJ/mol under the pressurized conditions, facilitating the ENRR process. We envisage that the cooperative regulations of catalysts and electrochemical devices open up the possibilities for industrially viable electrochemical ammonia production.

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