Nanozymes Inspired by Natural Enzymes

Accounts of Materials Research, Journal Year: 2021, Volume and Issue: 2(7), P. 534 - 547

Published: June 24, 2021

ConspectusNanozymes, nanomaterials with enzyme-like activities high structural stability, adjustable catalytic activity, functional diversity, recyclability, and feasibility in large-scale preparation, have become a hot spot the field of artificial enzymes recent years are expected to potential surrogates competitors for natural practical applications. With development in-depth research wide range application requirements, creating nanozymes performance comparable or even surpassing that has been key topic this field. Most reported past were obtained based on random synthesis screening, which efficiency is far inferior enzymes. Natural evolved over hundreds millions developed lot high-efficiency catalysis know-how hidden their features. To create highly active nanozymes, we assumed there general structure–activity relationship between proposed nanozyme optimization strategy by grafting principles into rational design nanozymes. On basis bioinspired strategy, series exhibit similar closer beyond those successfully synthesized. By now, rationally designed high-activity current nanozymes.In Account, focus representative progress systemic construction devoted introducing strategic concepts We show de novo simulating amino acid microenvironment using metal-free architecture coordination structure metal sites an effective significantly improving A future perspective challenges countermeasures these achievements. hope biologically inspired perception will arouse widespread interest fundamental applications as well provide inspiration

Language: Английский

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An Adjacent Atomic Platinum Site Enables Single‐Atom Iron with High Oxygen Reduction Reaction Performance

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(35), P. 19262 - 19271

Published: June 22, 2021

Abstract The modulation effect has been widely investigated to tune the electronic state of single‐atomic M‐N‐C catalysts enhance activity oxygen reduction reaction (ORR). However, in‐depth study is rarely reported for isolated dual‐atomic metal sites. Now, catalytic activities Fe‐N 4 moiety can be enhanced by adjacent Pt‐N through effect, in which acts as modulator 3d orbitals active site and optimize ORR activity. Inspired this principle, we design synthesize electrocatalyst that comprises /Pt‐N moieties dispersed nitrogen‐doped carbon matrix (Fe‐N @NC) exhibits a half‐wave potential 0.93 V vs. RHE negligible degradation (ΔE 1/2 =8 mV) after 10000 cycles 0.1 M KOH. We also demonstrate not effective optimizing performances Co‐N Mn‐N systems.

Language: Английский

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NiCo-Based Electrocatalysts for the Alkaline Oxygen Evolution Reaction: A Review

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(20), P. 12485 - 12509

Published: Sept. 27, 2021

Electrocatalytic water splitting is a sustainable way to produce hydrogen energy, but the oxygen evolution reaction (OER) at anode has sluggish kinetics and low energy conversion efficiency, which major bottleneck for large-scale production. The design synthesis of robust low-cost OER catalysts are crucial OER. NiCo-based electrocatalysts have suitable atomic electronic structures, show high activity stability during process. Recently, significant progress been made in regulating structure composition understanding nature catalysis, especially mechanism, catalytic active sites, structure–activity relationship. In this work, we summarized discussed latest development OER, with particular emphasis on catalyst synthesis, strategies boosting performance, catalysis from experimental theoretical perspectives. some descriptors, relationships based unveiled. Finally, challenges futuristic outlooks improving performance proposed, hope review can provide guidance more efficient electrocatalysts.

Language: Английский

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Altering Ligand Fields in Single-Atom Sites through Second-Shell Anion Modulation Boosts the Oxygen Reduction Reaction

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(5), P. 2197 - 2207

Published: Jan. 28, 2022

Single-atom catalysts based on metal-N4 moieties and anchored carbon supports (defined as M-N-C) are promising for oxygen reduction reaction (ORR). Among those, M-N-C with 4d 5d transition metal (TM4d,5d) centers much more durable not susceptible to the undesirable Fenton reaction, especially compared 3d ones. However, ORR activity of these TM4d,5d-N-C is still far from satisfactory; thus far, there few discussions about how accurately tune ligand fields single-atom TM4d,5d sites in order improve their catalytic properties. Herein, we leverage Ru-N-C a model system report an S-anion coordination strategy modulate catalyst's structure performance. The S anions identified bond N atoms second shell Ru centers, which allows us manipulate electronic configuration central sites. S-anion-coordinated catalyst delivers only but also outstanding long-term durability, superior those commercial Pt/C most near-term catalysts. DFT calculations reveal that high attributed lower adsorption energy intermediates at Metal-air batteries using this cathode side exhibit fast kinetics excellent stability.

Language: Английский

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Insight into Structural Evolution, Active Sites, and Stability of Heterogeneous Electrocatalysts

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(11)

Published: Sept. 7, 2021

Studying structure-activity correlations of electrocatalysts is essential for improving the conversion electrical to chemical energy. Recently, increasing evidence obtained by operando characterization techniques reveal that structural evolution catalysts caused interplay with electric fields, electrolytes and reactants/intermediates brings about formation real active sites. Hence, it time summarize related research advances envisage future developments. In this Minireview, we first introduce fundamental concepts associated (e.g., catalysts, sites/centers stability/lifetime) their relevance. Then, multiple triggers advanced characterizations are discussed. Significantly, a brief overview its reversibility in heterogeneous electrocatalysis provided, especially representative electrocatalytic oxygen reaction (OER) CO2 reduction (CO2 RR) processes. Lastly, key challenges opportunities exciting field highlighted.

Language: Английский

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A “Pre‐Constrained Metal Twins” Strategy to Prepare Efficient Dual‐Metal‐Atom Catalysts for Cooperative Oxygen Electrocatalysis

Advanced Materials, Journal Year: 2021, Volume and Issue: 34(7)

Published: Dec. 4, 2021

Dual-metal-atom-center catalysts (DACs) are a novel frontier in oxygen electrocatalysis, boasting functional and electronic synergies between contiguous metal centers higher catalytic activities than single-atom-center catalysts. However, the definition mechanism of DACs configurations remain unclear. Here, "pre-constrained twins" strategy is proposed to prepare FeN4 CoN4 with homogeneous conformations embedded N-doped graphitic carbon (FeCo-DACs/NC). A programmable phthalocyanines dimer used as structural moiety anchor bimetallic sites (containing Co Fe) metal-organic framework (MOF) achieve delocalized dispersion before pyrolysis. The resultant FeCo-DACs/NC exhibits excellent electrochemical performance electrocatalysis rechargeable Zn-air batteries. Theoretical calculations demonstrate that synergetic interaction adjacent metals optimizes d-band center position balances free energy *O intermediate, thereby improving electrocatalytic activity. This work opens up an avenue for rational design tailored structures uniform geometric configurations.

Language: Английский

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A durable half-metallic diatomic catalyst for efficient oxygen reduction

Energy & Environmental Science, Journal Year: 2022, Volume and Issue: 15(4), P. 1601 - 1610

Published: Jan. 1, 2022

By elaborately constructing a Fe–Zn based diatomic catalyst, the active center is changed from FeN 4– ZnN 4 to Zn–N 2 after protonation, leading well-maintained structure and thus high stability of ORR.

Language: Английский

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Long‐Range Interactions in Diatomic Catalysts Boosting Electrocatalysis

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(52)

Published: Oct. 6, 2022

Abstract The simultaneous presence of two active metal centres in diatomic catalysts (DACs) leads to the occurrence specific interactions between sites. Such interactions, referred as long‐range (LRIs), play an important role determining rate and selectivity a reaction. optimal combination must be determined achieve targeted efficiency. To date, various types DACs have been synthesised applied electrochemistry. However, LRIs not systematically summarised. Herein, regulation, mechanism, electrocatalytic applications are comprehensively summarised discussed. In addition basic information above, challenges, opportunities, future development proposed order present overall view reference for research.

Language: Английский

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Single‐atom catalysis for carbon neutrality

Carbon Energy, Journal Year: 2022, Volume and Issue: 4(6), P. 1021 - 1079

Published: July 14, 2022

Abstract Currently, more than 86% of global energy consumption is still mainly dependent on traditional fossil fuels, which causes resource scarcity and even emission high amounts carbon dioxide (CO 2 ), resulting in a severe “Greenhouse effect.” Considering this situation, the concept “carbon neutrality” has been put forward by 125 countries one after another. To achieve goals neutrality,” two main strategies to reduce CO emissions develop sustainable clean can be adopted. Notably, these are crucial for synthesis advanced single‐atom catalysts (SACs) energy‐related applications. In review, we highlight unique SACs conversion into high‐efficiency energy, example, through photocatalytic, electrocatalytic, thermal catalytic hydrogenation technologies, convert hydrocarbon fuels (CO, CH 4 , HCOOH, 3 OH, multicarbon [C 2+ ] products). addition, introduce technologies devices replace polluting such as photocatalytic electrocatalytic water splitting produce hydrogen oxygen reduction reaction (ORR) fuel cells. Impressively, several representative examples (including d ‐, ds p f ‐blocks) conversion, H ORR discussed describe methods, characterization, corresponding activity. Finally, review concludes with description challenges outlooks future applications contributing toward neutrality.

Language: Английский

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Implanting Single Zn Atoms Coupled with Metallic Co Nanoparticles into Porous Carbon Nanosheets Grafted with Carbon Nanotubes for High‐Performance Lithium‐Sulfur Batteries

Advanced Functional Materials, Journal Year: 2022, Volume and Issue: 32(20)

Published: Feb. 12, 2022

Abstract The electrochemical performance of lithium‐sulfur (Li‐S) batteries is severely hindered by the sluggish sulfur redox kinetics and shuttle effect lithium polysulfides (LiPSs). Herein, an integrated composite catalyst consisting Co nanoparticles single‐atom (SA) Zn co‐implanted in nitrogen‐doped porous carbon nanosheets grafted with nanotubes (Co/SA‐Zn@N‐C/CNTs) rationally developed toward this challenge. Experimental theoretical investigations indicate that synergistically dual active sites atomic Zn‐N 4 moieties optimal charge redistribution not only strongly confine LiPSs but also effectively catalyze its conversion reactions lowering energy barrier from Li 2 S to while N‐doped carbon‐grafted CNTs enables a large surface area for more site exposure provides fast electron/ion pathway. Benefiting synergies, Li‐S equipped Co/SA‐Zn@N‐C/CNTs‐based cathode exhibit high reversible capacity 1302 mAh g −1 at 0.2 C low fading rate 0.033% per cycle over 800 cycles 1 C. Moreover, areal 4.5 cm −2 loading 5.1 mg can be achieved. present work may provide new insight into design high‐performance sulfur‐based cathodes batteries.

Language: Английский

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