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

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(12), P. 5709 - 5721

Published: Feb. 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.

Language: Английский

---

Modulating the local coordination environment of single-atom catalysts for enhanced catalytic performance

Nano Research, Journal Year: 2020, Volume and Issue: 13(7), P. 1842 - 1855

Published: March 30, 2020

Language: Английский

---

Recent advances of noble-metal-free bifunctional oxygen reduction and evolution electrocatalysts

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(13), P. 7745 - 7778

Published: Jan. 1, 2021

Bifunctional oxygen reduction and evolution constitute the core processes for sustainable energy storage. The advances on noble-metal-free bifunctional electrocatalysts are reviewed.

Language: Английский

---

Engineering Dual Single‐Atom Sites on 2D Ultrathin N‐doped Carbon Nanosheets Attaining Ultra‐Low‐Temperature Zinc‐Air Battery

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(12)

Published: Jan. 7, 2022

Herein, a novel dual single-atom catalyst comprising adjacent Fe-N4 and Mn-N4 sites on 2D ultrathin N-doped carbon nanosheets with porous structure (FeMn-DSAC) was constructed as the cathode for flexible low-temperature Zn-air battery (ZAB). FeMn-DSAC exhibits remarkable bifunctional activities oxygen reduction reaction (ORR) evolution (OER). Control experiments density functional theory calculations reveal that catalytic activity arises from cooperative effect of Fe/Mn dual-sites aiding *OOH dissociation well nanosheet promoting active sits exposure mass transfer during process. The excellent enables ZAB to operate efficiently at ultra-low temperature -40 °C, delivering 30 mW cm-2 peak power retaining up 86 % specific capacity room counterpart.

Language: Английский

---

Dual Single‐Atomic Ni‐N₄ and Fe‐N₄ Sites Constructing Janus Hollow Graphene for Selective Oxygen Electrocatalysis

Advanced Materials, Journal Year: 2020, Volume and Issue: 32(30)

Published: June 22, 2020

Nitrogen-coordinated metal single atoms in carbon have aroused extensive interest recently and been growing as an active research frontier a wide range of key renewable energy reactions devices. Herein, step-by-step self-assembly strategy is developed to allocate nickel (Ni) iron (Fe) respectively on the inner outer walls graphene hollow nanospheres (GHSs), realizing separate-sided different single-atom functionalization graphene. The Ni or Fe atom demonstrated be coordinated with four N via formation Ni-N4 Fe-N4 planar configuration. /GHSs/Fe-N4 Janus material exhibits excellent bifunctional electrocatalytic performance, which clusters dominantly contribute high activity toward oxygen reduction reaction (ORR), while are responsible for evolution (OER). Density functional theory calculations demonstrate structures reactivities ORR OER. endows rechargeable Zn-air battery efficiency cycling stability air-cathode, outperforming that benchmark Pt/C+RuO2 air-cathode. current work paves new avenue precise control sites surface high-performance selective electrocatalysts.

Language: Английский

---

Surface Coordination Chemistry of Atomically Dispersed Metal Catalysts

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(21), P. 11810 - 11899

Published: Aug. 13, 2020

Atomically dispersed metal catalysts (ADCs), as an emerging class of heterogeneous catalysts, have been widely investigated during the past two decades. The atomic dispersion nature catalytic centers makes them ideal system for bridging homogeneous and catalysts. recent rapid development new synthetic strategies has led to explosive growth ADCs with a wide spectrum atoms on supports different chemical compositions natures. availability diverse creates powerful materials platform investigating mechanisms complicated catalysis at levels. Considering most are coordinated by donors from supports, this review will demonstrate how surface coordination chemistry plays important role in determining performance ADCs. This start link between catalysis. After brief description advantages limitations common structure characterization methods ADCs, types be discussed. We mainly illustrate local vicinal species support systems act together center determine activity, selectivity, stability dynamic change highlighted. At end review, personal perspectives further field provided.

Language: Английский

---

Orbital coupling of hetero-diatomic nickel-iron site for bifunctional electrocatalysis of CO2 reduction and oxygen evolution

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: July 2, 2021

While inheriting the exceptional merits of single atom catalysts, diatomic site catalysts (DASCs) utilize two adjacent atomic metal species for their complementary functionalities and synergistic actions. Herein, a DASC consisting nickel-iron hetero-diatomic pairs anchored on nitrogen-doped graphene is synthesized. It exhibits extraordinary electrocatalytic activities stability both CO

Language: Английский

---

Emerging Dual‐Atomic‐Site Catalysts for Efficient Energy Catalysis

Advanced Materials, Journal Year: 2021, Volume and Issue: 33(36)

Published: July 23, 2021

Atomically dispersed metal catalysts with well-defined structures have been the research hotspot in heterogeneous catalysis because of their high atomic utilization efficiency, outstanding activity, and selectivity. Dual-atomic-site (DASCs), as an extension single-atom (SACs), recently drawn surging attention. The DASCs possess higher loading, more sophisticated flexible active sites, offering chance for achieving better catalytic performance, compared SACs. In this review, recent advances on how to design new enhancing energy will be highlighted. It start classification marriage two kinds homonuclear heteronuclear according configuration sites. Then, state-of-the-art characterization techniques discussed. Different synthetic methods applications various reactions, including oxygen reduction reaction, carbon dioxide monoxide oxidation others followed. Finally, major challenges perspectives provided.

Language: Английский

---

Coordination Engineering of Single‐Atom Catalysts for the Oxygen Reduction Reaction: A Review

Advanced Energy Materials, Journal Year: 2020, Volume and Issue: 11(3)

Published: Nov. 30, 2020

Abstract Future renewable energy supplies and a sustainable environment rely on many important catalytic processes. Single‐atom catalysts (SACs) are attractive because of their maximum atom utilization efficiency, tunable electronic structures, outstanding performance. Of particular note, transition‐metal SACs exhibit excellent activity selectivity for the oxygen reduction reaction (ORR)—an half in fuel cells metal–air batteries as well portable hydrogen peroxide (H 2 O ) production. Although considerable efforts have been made synthesis ORR, regulation coordination environments thus structures still pose big challenge. In this review, strategies manipulating classified into three categories, including center metal atoms, manipulation surrounding connecting to atom, modification geometric configuration support. Finally, some issues regarding future development ORR raised possible solutions proposed.

Language: Английский

---

Atomically Dispersed Fe–Co Dual Metal Sites as Bifunctional Oxygen Electrocatalysts for Rechargeable and Flexible Zn–Air Batteries

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(2), P. 1216 - 1227

Published: Jan. 5, 2022

Single-metal site catalysts have exhibited highly efficient electrocatalytic properties due to their unique coordination environments and adjustable local structures for reactant adsorption electron transfer. They been widely studied many electrochemical reactions, including oxygen reduction reaction (ORR) evolution (OER). However, it remains a significant challenge realize high-efficiency bifunctional catalysis (ORR/OER) with single-metal-type active sites. Herein, we report atomically dispersed Fe–Co dual metal sites (FeCo–NC) derived from Fe Co co-doped zeolitic imidazolate frameworks (ZIF-8s), aiming build up multiple ORR/OER catalysts. The FeCo–NC catalyst shows excellent catalytic activity in alkaline media the ORR (E1/2 = 0.877 V) OER (Ej=10 1.579 V). Moreover, its outstanding stability during is comparable noble-metal (Pt/C RuO2). atomic dispersion state, structure, charge density difference of were characterized determined using advanced physical characterization functional theory (DFT) calculations. FeCo–N6 moieties are likely main simultaneously improved performance relative traditional single We further incorporated into an air electrode fabricating rechargeable flexible Zn–air batteries, generating superior power (372 mW cm–2) long-cycle (over 190 h) stability. This work would provide method design synthesize multi-metal electrocatalysis.

Language: Английский

---