Rare earth La single atoms supported MoO3-x for efficient photocatalytic nitrogen fixation

Liu, Xiufan; Luo, Yani; Ling, Cancan; Shi, Yanbiao; Zhan, Guangming; Li, Hao; Gu, Huayu; Wei, Kai; Guo, Fang; Ai, Zhihui; Zhang, Lizhi

doi:10.1016/j.apcatb.2021.120766

Cited by 103 publications

(95 citation statements)

References 32 publications

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“…This signifies that the heteroatoms are indeed doped into the graphite lattices in the surface layers of CB, which break the ordered hexagonal carbon structures [28] . On the other hand, Gd atoms exhibit no crystallographic characteristics in the XRD patterns of CBNGd‐700 and CBNNiGd‐700 (Figure 2a), which may stem from the superb dispersion of atomic Gd on the supports [20] . Interestingly, the existence of Gd atoms in CBNNiGd‐700 affects the Ni crystal structure.…”

Section: Resultsmentioning

confidence: 99%

“…On the contrary, the graphite stripes disappear and the new Ni (111) crystal planes emerge in CBNNiGd‐700 and CBNNi‐700, implying that Ni with the relatively small atomic radius is readily incorporated into the graphite lattices of CB, which can generate defect sites [23] . As revealed by the elemental mapping images, Ni atoms agglomerate into nanoparticles encapsulated in the carbon matrixes of CBNNiGd‐700 and CBNNi‐700, [11] while the relatively uniform dispersion of Gd atoms is accomplished within CBNNiGd‐700 and CBNGd‐700 [20, 24] . It is noteworthy that partial Gd atoms in CBNNiGd‐700 gather around Ni nanoparticles and that the sizes of Ni nanoparticles in CBNNiGd‐700 are significantly smaller than in CBNNi‐700.…”

Section: Resultsmentioning

confidence: 99%

“…[19] In the meantime, the strong lanthanide contraction effect of LM atoms can change the local electron densities of the surrounding atoms and optimize the electronic states of the supports, in favor of the elevation of adsorption capabilities of catalyst surfaces and thereby the strengthening of catalytic performance. [20] Accordingly, the incorporation of LMs into TMs-based catalysts may not only regulate the agglomeration degree of TM nanoparticles but also engineer the local electron structures of TM 3d orbitals, thereby realizing both high current densities and excellent CO selectivities in ECR. To our knowledge, the LMs-doped TMs-based catalysts have yet to be systematically investigated in the field of electrochemical conversion of CO 2 .…”

Section: Introductionmentioning

confidence: 99%

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Gadolinium Changes the Local Electron Densities of Nickel 3d Orbitals for Efficient Electrocatalytic CO₂ Reduction

et al. 2022

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Generally, in terms of electrocatalytic CO 2 reduction, single-atom catalysts show high selectivities yet low current densities whereas conventional nanoparticle catalysts exhibit relatively high current densities but low selectivities. This work combines the advantages of the two classes of catalysts by constructing a Ni-Gd-N-doped carbon black electrocatalyst within which Ni I active sites are exposed outside the carbon layers and Ni nanoparticles are encapsulated inside the carbon layers. The Gd atoms can not only influence the local electron densities of Ni 3d orbitals, thus strengthening the electronic activity, but also tailor the sizes of the Ni nanoparticles, thereby minimizing the activity toward hydrogen evolution. Accordingly, this electrocatalyst yields both a high CO faradaic efficiency (97 %) and a large current density (308 mA cm À 2 ), alongside an outstanding stability (100 h).

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Gadolinium Changes the Local Electron Densities of Nickel 3d Orbitals for Efficient Electrocatalytic CO₂ Reduction

et al. 2022

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“…The advantage of bulk materials as supports for RE SACs is that the difference in coordination number between the inner bulk and the surface provides the ability to trap RE species and reduce the surface energy, especially at surface defects or vacancy sites. [ 164 ] For example, the oxygen vacancies in MoO 3− x can be utilized to trap La atoms to create La/MoO 3− x , [ 102 ] and the use of photodeposition can also result in the formation of atomic La species trapped by oxygen defects in MoO 3− x . In these structures, the bulk Mo and O atoms form sixfold (Mo 6c ) and threefold (O 3c ) coordinated structures, but oxygen vacancies at the Mo 6c sites result in the formation of unsaturated Mo 5c and O 2c sites that are thermodynamically favorable trapping sites for La atoms.…”

Section: Synthetic Methods For Re Sacsmentioning

confidence: 99%

Rare‐Earth Single‐Atom Catalysts: A New Frontier in Photo/Electrocatalysis

Wang

Zhu

et al. 2022

Small Methods

Self Cite

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through three steps: 1) at the catalyst surface, the reactants diffuse toward the active sites; 2) the reactants are adsorbed at the active sites and transformed into products via consecutive elementary reaction steps; 3) the products diffuse from the surface via chemical desorption. [4][5][6] To facilitate this transformational process, the catalytically active surface should contain many highly catalytically active sites. [7][8][9][10] However, in conventional bulk catalysts, typically, only a few surface atoms provide catalytic activity, and most of the subsurface atoms cannot directly participate in the reactions, thus resulting in atomic waste. [11][12][13][14][15] Recently, more efficient catalysts have been prepared by changing the active sites from those of a bulk catalyst to isolated atoms; these systems are known as single-atom catalysts (SACs). Thus, the term SAC is given to materials whose catalytically active sites are single atoms. The first discussion of SACs can be traced back to 2011, Zhang et al. reported Pt atoms anchored on FeO x (Pt 1 /FeO x ) for CO oxidation. [16] Crucially, when the size of catalysts reaches the atomic scale, distinctive properties that affect their chemical activities, conversion efficiencies, and stabilities emerge. In particular, unlike bulk catalysts, SACs maximize the use of the catalytically active metal atoms (nearly 100% atom efficiency). [17][18][19][20] Further, compared with bulk catalysts, SACs have unique advantages: 1) an unsaturated coordination environment that affects the affinity of the catalyst for intermediate species; 2) distinctive quantum size effects that yield discrete energy levels and frontier molecular orbital (FMO) occupancies; 3) strong atom support interactions that facilitate surface charge redistribution; 4) appropriate polarity to restrain shuttle effects during catalytic processes; 5) breaking of the energy scaling relationship based on the Sabatier principle for enhanced catalytic activity; and 6) site-to-site interactions between single atoms that enhance the catalytic kinetics. [21][22][23][24][25][26][27][28] In recent years, the use of transition-metal-based SACs [29][30][31] and precious-metal-based SACs [32][33][34] has developed rapidly, especially in the field of energy catalysis. In particular, research has focused on Fe, [35][36][37] Co, [38,39] Ni, [40,41] Mn, [42] Pt, [43,44] Ir, [45][46][47] Pd. [48,49] Owing to the strong atom-support interactions, the coupling of the metal and ligand orbitals in the support can result in changes in the d-band center (ε d ) of the metal atoms, [50,51] and this spin-orbit coupling, which results in a range of electronic states, is key to the success of heterogeneous Single-atom catalysts (SACs) provide well-defined active sites with 100% atom utilization, and can be prepared using a wide range of support materials. Therefore, they are attracting global attention, especially in the fields of energy conversion and storage. To date, research has focused on transitionmetal and precious-metal-bas...

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“…As the foundation of N 2 molecule activation involves the electron back-donation into the antibonding orbitals of the adsorbate, its prerequisite to achieving e cacious pNRR is to create excellent adsorption sites 9,10 . Hence, the activity of pNRR is largely reliant upon that adsorption mode of N 2 molecules on the surface active sites of photocatalyst 11 .…”

Section: Introductionmentioning

confidence: 99%

Regulating bimetallic active centers for exploring the structure-activity relationship upon high-performance photocatalytic nitrogen reduction

Zhang

Gao

Han

et al. 2022

Preprint

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Photocatalytic ammonia (NH3) synthesis from N2 is a strategy conducive to carbon neutrality because it avoids high energy consumption and high carbon emission process in the industrial synthesis of NH3. However, the structure-activity relationship of bimetallic active centers in heterogeneous catalysts is still dimness for high-performance photocatalytic nitrogen reduction reaction (pNRR). Here, a rational N2-bridging strategy for heterogeneously pNRR has been expanded through regulating bimetallic Ti-Pd active centers at TiO2 (101)/Pd (111) interface and the structure-activity correlation during the pNRR was explored. The side-on adsorption with “*N ≡ N*” configuration (*presents the adsorption site) on Ti-Pd centers induces a considerable polarization and potent activation of N2, enabling to achieve an impressive rate of NH3 production (635.73 µg gcat.−1 h− 1) on the optimal se-Pd/m-TiO2 NRs (2.71%). More importantly, nearly ~ 92.37% of initial activity could be retained following 8 successive reaction rounds. Further mechanism studies revealed that the side-on bridging mode of N2 with bimetallic Ti-Pd centers possesses an ultra-high adsorption energy, which can effectively weaken the triple bond of N2 and reduce the activation energy barrier of pNRR process. This study provides insights into the electronic structure regulation of bimetallic active centers and structure-property relationship at the atomic level.

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Rare earth La single atoms supported MoO3-x for efficient photocatalytic nitrogen fixation

Cited by 103 publications

References 32 publications

Gadolinium Changes the Local Electron Densities of Nickel 3d Orbitals for Efficient Electrocatalytic CO₂ Reduction

Gadolinium Changes the Local Electron Densities of Nickel 3d Orbitals for Efficient Electrocatalytic CO₂ Reduction

Rare‐Earth Single‐Atom Catalysts: A New Frontier in Photo/Electrocatalysis

Regulating bimetallic active centers for exploring the structure-activity relationship upon high-performance photocatalytic nitrogen reduction

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Rare earth La single atoms supported MoO3-x for efficient photocatalytic nitrogen fixation

Cited by 103 publications

References 32 publications

Gadolinium Changes the Local Electron Densities of Nickel 3d Orbitals for Efficient Electrocatalytic CO2 Reduction

Gadolinium Changes the Local Electron Densities of Nickel 3d Orbitals for Efficient Electrocatalytic CO2 Reduction

Rare‐Earth Single‐Atom Catalysts: A New Frontier in Photo/Electrocatalysis

Regulating bimetallic active centers for exploring the structure-activity relationship upon high-performance photocatalytic nitrogen reduction

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Product

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Gadolinium Changes the Local Electron Densities of Nickel 3d Orbitals for Efficient Electrocatalytic CO₂ Reduction

Gadolinium Changes the Local Electron Densities of Nickel 3d Orbitals for Efficient Electrocatalytic CO₂ Reduction