Single-Atom Catalysts across the Periodic Table

Chemical Reviews, Год журнала: 2020, Номер 120(21), С. 11703 - 11809

Опубликована: Окт. 21, 2020

Isolated atoms featuring unique reactivity are at the heart of enzymatic and homogeneous catalysts. In contrast, although concept has long existed, single-atom heterogeneous catalysts (SACs) have only recently gained prominence. Host materials similar functions to ligands in catalysts, determining stability, local environment, electronic properties isolated thus providing a platform for tailoring targeted applications. Within just decade, we witnessed many examples SACs both disrupting diverse fields catalysis with their distinctive substantially enriching our understanding molecular processes on surfaces. To date, term SAC mostly refers late transition metal-based systems, but numerous exist which other elements play key catalytic roles. This review provides compositional encyclopedia SACs, celebrating 10th anniversary introduction this term. By defining broadest sense, explore full elemental diversity, joining different areas across whole periodic table, discussing historical milestones recent developments. particular, examine coordination structures associated accessed through distinct single-atom–host combinations relate them main applications thermo-, electro-, photocatalysis, revealing trends element-specific evolution, host design, uses. Finally, highlight frontiers field, including multimetallic atom proximity control, possible multistep cascade reactions, identifying challenges, propose directions future development flourishing field.

Язык: Английский

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Tackling the Activity and Selectivity Challenges of Electrocatalysts toward the Nitrogen Reduction Reaction via Atomically Dispersed Biatom Catalysts

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(12), С. 5709 - 5721

Опубликована: Фев. 18, 2020

Developing efficient catalysts for nitrogen fixation is becoming increasingly important but still challenging due to the lack of robust design criteria tackling activity and selectivity problems, especially electrochemical reduction reaction (NRR). Herein, by means large-scale density functional theory (DFT) computations, we reported a descriptor-based principle explore large composition space two-dimensional (2D) biatom (BACs), namely, metal dimers supported on 2D expanded phthalocyanine (M2-Pc or MM'-Pc), toward NRR at acid conditions. We sampled both homonuclear (M2-Pc) heteronuclear (MM'-Pc) BACs constructed map using N2H* adsorption energy as descriptor, which reduces number promising catalyst candidates from over 900 less than 100. This strategy allowed us readily identify 3 28 BACs, could break metal-based benchmark NRR. Particularly, free difference H* screened out five systems, including Ti2-Pc, V2-Pc, TiV-Pc, VCr-Pc, VTa-Pc, exhibit strong capability suppressing competitive hydrogen evolution (HER) with favorable limiting potential -0.75, -0.39, -0.74, -0.85, -0.47 V, respectively. work not only broadens possibility discovering more N2 also provides feasible rational electrocatalysts helps pave way fast screening other reactions.

Язык: Английский

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Building Up a Picture of the Electrocatalytic Nitrogen Reduction Activity of Transition Metal Single-Atom Catalysts

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(24), С. 9664 - 9672

Опубликована: Май 30, 2019

The lack of chemical understanding and efficient catalysts impedes the development electrocatalytic nitrogen reduction reaction (eNRR) for ammonia production. In this work, we employed density functional theory calculations to build up a picture (activity trends, electronic origins, design strategies) single-atom (SACs) supported on nitrogen-doped carbons as eNRR electrocatalysts. To construct such picture, work presents systematic studies activity SACs covering 20 different transition metal (TM) centers coordinated by atoms contained in three types carbon substrates, which gives 60 SACs. Our study shows that intrinsic trends could be established basis adatom adsorption energy (ΔEN*). Furthermore, influence support (ligands) ΔEN* proved related bonding/antibonding orbital population regulating scaling relations intermediates, respectively. Accordingly, two-step strategy is proposed improving eNNR TM-SACs, involves following: (i) selection most promising family (g-C3N4 predicted work) (ii) further improvement best candidate aforementioned via tuning strength key intermediates. Also, stability N-doped supports their selectivity comparison competing hydrogen evolution need taken into consideration screening durable candidates. Finally, an effective designing active, stable, selective based mechanistic insights elaborated guide future studies.

Язык: Английский

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Self-adaptive dual-metal-site pairs in metal-organic frameworks for selective CO2 photoreduction to CH4

Nature Catalysis, Год журнала: 2021, Номер 4(8), С. 719 - 729

Опубликована: Авг. 19, 2021

Язык: Английский

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Single-Boron Catalysts for Nitrogen Reduction Reaction

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(7), С. 2884 - 2888

Опубликована: Фев. 5, 2019

Boron has been explored as p-block catalysts for nitrogen reduction reaction (NRR) by density functional theory. Unlike transition metals, on which the active centers need empty d orbitals to accept lone-pair electrons of molecule, sp3 hybrid orbital boron atom can form B-to-N π-back bonding. This results in population N-N π* and concomitant decrease bond order. We demonstrate that catalytic activity is highly correlated with degree charge transfer between substrate. Among 21 concept-catalysts, single atoms supported graphene substituted into h-MoS2 are identified most promising NRR catalysts, offering excellent energy efficiency selectivity against hydrogen evolution reaction.

Язык: Английский

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Highly Efficient and Selective Generation of Ammonia and Hydrogen on a Graphdiyne-Based Catalyst

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(27), С. 10677 - 10683

Опубликована: Май 31, 2019

The emergence of zerovalent atom catalysts has been highly attractive for catalytic science. For many years, scientists have explored the stability and demonstrated their unique properties. Here, we describe an catalyst (AC) with atomically dispersed molybdenum atoms on graphdiyne (Mo0/GDY) a high mass content Mo (up to 7.5 wt %) that was synthesized via facile scalable process. shows both excellent selectivity activity in electrochemical reduction nitrogen hydrogen evolution reaction aqueous solutions at room temperature pressure. It is noted this first bifunctional AC efficient selective ammonia generation. process our well understood, structure defined, performance excellent, providing solid foundation generation application new catalysts.

Язык: Английский

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Nitrogen Vacancies on 2D Layered W₂N₃: A Stable and Efficient Active Site for Nitrogen Reduction Reaction

Advanced Materials, Год журнала: 2019, Номер 31(32)

Опубликована: Июнь 13, 2019

Abstract Electrochemical nitrogen reduction reaction (NRR) under ambient conditions provides an avenue to produce carbon‐free hydrogen carriers. However, the selectivity and activity of NRR are still hindered by sluggish kinetics. Nitrogen Vacancies on transition metal nitrides considered as one most ideal active sites for virtue their unique vacancy properties such appropriate adsorption energy dinitrogen molecule. catalytic performance is usually limited unstable feature. Herein, a new 2D layered W 2 N 3 nanosheet prepared vacancies demonstrated be electrochemical with steady ammonia production rate 11.66 ± 0.98 µg h −1 mg cata (3.80 0.32 × 10 −11 mol cm −2 s ) Faradaic efficiency 11.67 0.93% at −0.2 V versus reversible electrode 12 cycles (24 h). A series ex situ synchrotron‐based characterizations prove that stable high valence state tungsten atoms confinement effect. Density function theory calculations suggest can provide electron‐deficient environment which not only facilitates adsorption, but also lowers thermodynamic limiting potential NRR.

Язык: Английский

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Synthesis of Leaf‐Vein‐Like g‐C₃N₄ with Tunable Band Structures and Charge Transfer Properties for Selective Photocatalytic H₂O₂ Evolution

Advanced Functional Materials, Год журнала: 2020, Номер 30(39)

Опубликована: Авг. 12, 2020

Abstract Photocatalytic H 2 O evolution through two‐electron oxygen reduction has attracted wide attention as an environmentally friendly strategy compared with the traditional anthraquinone or electrocatalytic method. Herein, a biomimetic leaf‐vein‐like g‐C 3 N 4 efficient photocatalyst for is reported, which owns tenable band structure, optimized charge transfer, and selective reduction. The mechanism regulation of structure transfer well studied by combining experiments theoretical calculations. yield CN4 (287 µmol h −1 ) about 3.3 times higher than that pristine CN (87 ), apparent quantum over reaches 27.8% at 420 nm, much many other current photocatalysts. This work not only provides novel design excellent efficiency, but also promotes deep understanding role defect doping sites on photocatalytic activity.

Язык: Английский

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MXene-based photocatalysts

Journal of Material Science and Technology, Год журнала: 2020, Номер 56, С. 18 - 44

Опубликована: Март 18, 2020

Язык: Английский

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A General Two‐Step Strategy–Based High‐Throughput Screening of Single Atom Catalysts for Nitrogen Fixation

Small Methods, Год журнала: 2018, Номер 3(9)

Опубликована: Дек. 13, 2018

Abstract Electrocatalytic or photocatalytic N 2 reduction holds great promise for green and sustainable NH 3 production under ambient conditions, where an efficient catalyst plays a crucial role but remains long‐standing challenge. Here, high‐throughput screening of catalysts among (nitrogen‐doped) graphene‐supported single atom is performed based on general two‐step strategy. 10 promising candidates with excellent performance are extracted from 540 systems. Most strikingly, W embedded in graphene three C coordination (W 1 ) exhibits the best extremely low onset potential 0.25 V. This study not only provides series fixation, also paves new way rational design fixation conditions.

Язык: Английский

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