Defect Engineering in Photocatalytic Nitrogen Fixation

ACS Catalysis, Journal Year: 2019, Volume and Issue: 9(11), P. 9739 - 9750

Published: Sept. 17, 2019

Approximately 2% of the energy consumed by humans each year is used to make nitrogen-based fertilizers, with ammonia (NH3) production being most significant contributor this demand. Currently, NH3 synthesized Haber–Bosch process, an energy-intensive synthesis requiring both high temperatures (400–500 °C) and pressures (150–250 atm) achieve meaningful rates N2 conversion. As a means reducing input carbon footprint synthesis, researchers are now seeking more environmentally friendly approaches for fixation. Photocatalytic using sunlight semiconductor photocatalyst, represents one promising strategies (typically employing water as agent). Rates photocatalytic currently too low justify serious practical consideration, which can be traced sluggish adsorption/activation kinetics molecule on catalyst surfaces under ambient temperature pressure conditions. Recent studies have highlighted potential defect engineering boosting light-harvesting, charge separation, adsorption characteristics photocatalysts in reductive processes such splitting CO2 reduction. Herein, we explore similarly enhance Special emphasis placed structure modulation (especially 2D materials porous structures) interface (including vacancy creation, metal doping, strain) enhancing activation The overarching aim Perspective provide snapshot recent breakthroughs rational design thus providing useful scaffold future research very exciting emerging field.

Language: Английский

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Theoretical insights into single-atom catalysts

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(22), P. 8156 - 8178

Published: Jan. 1, 2020

Single-atom catalysts (SACs) with atomically dispersed metals have emerged as a new class of heterogeneous and attracted considerable interest because they offer 100% metal atom utilization show excellent catalytic behavior compared traditionally supported nano-particles. However, it is challenging to explore the active sites mechanisms SACs through common characterization methods due isolated single atoms. Therefore, employing theoretical calculations determine nature SACs' reaction particularly meaningful. This paper describes by summarizing diverse applications properties SACs, which starts from computational simulation on couple important SACs. Then distinctive fundamental are discussed. At last, challenges future perspectives for outlined.

Language: Английский

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Non-aqueous gas diffusion electrodes for rapid ammonia synthesis from nitrogen and water-splitting-derived hydrogen

Nature Catalysis, Journal Year: 2020, Volume and Issue: 3(5), P. 463 - 469

Published: May 4, 2020

Language: Английский

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Recent advances in nanostructured heterogeneous catalysts for N-cycle electrocatalysis

Deleted Journal, Journal Year: 2022, Volume and Issue: 1, P. e9120010 - e9120010

Published: May 30, 2022

To restore the natural nitrogen cycle (N-cycle), artificial N-cycle electrocatalysis with flexibility, sustainability, and compatibility can convert intermittent renewable energy (e.g., wind) to harmful or value-added chemicals minimal carbon emissions. The background of such N-cycles, as fixation, ammonia oxidation, nitrate reduction, is briefly introduced here. discussion emerging nanostructures in various conversion reactions focused on architecture/compositional design, electrochemical performances, reaction mechanisms, instructive tests. Energy device advancements for achieving more functions well in situ/operando characterizations toward understanding key steps are also highlighted. Furthermore, some recently proposed less discussed C–N coupling summarized. We classify inorganic sources that each other under an applied voltage into three types, namely, abundant nitrogen, toxic (nitrite), oxides, useful compounds ammonia, hydrazine, hydroxylamine, goal providing critical insights strategies facilitate development our circular economy.

Language: Английский

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Engineering Local Coordination Environments of Atomically Dispersed and Heteroatom‐Coordinated Single Metal Site Electrocatalysts for Clean Energy‐Conversion

Advanced Energy Materials, Journal Year: 2019, Volume and Issue: 10(11)

Published: Dec. 20, 2019

Abstract Carbon‐based heteroatom‐coordinated single‐atom catalysts (SACs) are promising candidates for energy‐related electrocatalysts because of their low‐cost, tunable catalytic activity/selectivity, and relatively homogeneous morphologies. Unique interactions between single metal sites surrounding coordination environments play a significant role in modulating the electronic structure centers, leading to unusual scaling relationships, new reaction mechanisms, improved performance. This review summarizes recent advancements engineering local environment SACs electrocatalytic performance several crucial energy‐convention electrochemical reactions: oxygen reduction reaction, hydrogen evolution CO 2 nitrogen reaction. Various strategies including heteroatom‐doping, changing location on support, introducing external ligands, constructing dual comprehensively discussed. The controllable synthetic methods activity enhancement mechanism state‐of‐the‐art also highlighted. Recent achievements modification will provide an understanding structure–activity relationship rational design advanced electrocatalysts.

Language: Английский

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Rational Catalyst Design for N₂ Reduction under Ambient Conditions: Strategies toward Enhanced Conversion Efficiency

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(12), P. 6870 - 6899

Published: May 26, 2020

Ammonia (NH3), one of the basic chemicals in most fertilizers and a promising carbon-free energy storage carrier, is typically synthesized via Haber–Bosch process with high consumption massive emission greenhouse gases. The photo/electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions has attracted increasing interests recently, providing alternative routes to realize green NH3 synthesis. Despite rapid advances achieved this attractive research field, unsatisfactory conversion efficiency including low yield rate, limited Faradaic or apparent quantum still remains as great challenge. NRR performance intrinsically related electronic surface structure catalysts. Rational design preparation advanced catalysts are indispensable improve (e.g., activity selectivity) NRR. In Review, various strategies for development desirable comprehensively summarized, mainly containing defect engineering, structural manipulation, crystallographic tailoring, interface regulation. State-of-the-art heterogeneous catalysts, prevailing theories underlying catalytic mechanisms, together current issues, critical challenges, perspectives discussed. It highly expected that Review will promote understanding recent area stimulate greater designing future.

Language: Английский

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Density Functional Theory Calculations for Insight into the Heterocatalyst Reactivity and Mechanism in Persulfate-Based Advanced Oxidation Reactions

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(17), P. 11129 - 11159

Published: Aug. 23, 2021

Advanced oxidation processes (AOPs) based on persulfates such as peroxymonosulfate and peroxydisulfate via heterogeneous catalysts have been a research hotspot due to their outstanding performances in removing emerging organic contaminants (OCs). In this Review, we highlight the recent advances theoretical simulations for persulfate-based AOPs (PS-AOPs) using density functional theory (DFT), with emphasis catalyst properties mechanism of persulfate activation over variety (including nanocarbons, metals, metal oxides). Moreover, OCs degradation by diverse reactive oxygen species investigated computations are also summarized. The descriptors computational studies related structure–performance relationships discussed. Finally, challenges future focuses DFT PS-AOPs proposed, including evaluation properties, elucidation mechanism, especially nonradical pathway, rational design on-demand catalysts.

Language: Английский

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Self-Adjusting Activity Induced by Intrinsic Reaction Intermediate in Fe–N–C Single-Atom Catalysts

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(36), P. 14115 - 14119

Published: Aug. 30, 2019

Fe-N-C single-atom catalysts (SACs) exhibit high activity for oxygen reduction reaction (ORR). However, it remains controversial how the active center mediates catalysis, and predicted potential deviates from experimental results, hindering development of ideal SACs. Here, using first-principles calculations, we present a microkinetic model ORR on SACs, disclosing self-adjusting mechanism induced by its intrinsic intermediate. The modeling results show that Fe site FeN4 is covered with an intermediate OH* 0.28 to 1.00 V. Remarkably, such becomes part moiety, Fe(OH)N4, can optimize bindings site, exhibiting theoretical half-wave ∼0.88 Partial current density analysis reveals dominating associative path over dissociative ones. In addition, Mn-N-C Co-N-C SACs unveiled. This work demonstrates necessity assessing effect intermediates in catalysis provides practical guidance rational design high-performance

Language: Английский

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Microenvironment modulation of single-atom catalysts and their roles in electrochemical energy conversion

Science Advances, Journal Year: 2020, Volume and Issue: 6(39)

Published: Sept. 24, 2020

Microenvironment engineering of single-atom catalysts paves the way toward efficient electrochemical energy conversion.

Language: Английский

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Bimetallic metal–organic frameworks and MOF-derived composites: Recent progress on electro- and photoelectrocatalytic applications

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 451, P. 214264 - 214264

Published: Oct. 25, 2021

Language: Английский

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