Recent Advances in Mechanistic Understanding of Metal-Free Carbon Thermocatalysis and Electrocatalysis with Model Molecules

Metal-free carbon,as the most representative heterogeneous metal-free catalysts,have received considerable interests in electro-and thermo-catalytic reac-tions due to their impressive performance and sustainability.Over the past decade,well-designed carbon catalysts with tunable structures and heteroatom groups coupled with various characterization techniques have proposed numerous reaction mechanisms.However,active sites,key intermediate species,precise structure-activity relationships and dynamic evolution processes of carbon catalysts are still rife with controversies due to the monotony and limitation of used experimental methods.In this Review,we sum-marize the extensive efforts on model catalysts since the 2000s,particularly in the past decade,to overcome the influences of material and structure limitations in metal-free carbon catalysis.Using both nanomolecule model and bulk model,the real contribution of each alien species,defect and edge configuration to a series of fundamentally important reactions,such as thermocatalytic reactions,electrocatalytic reactions,were systematically studied.Combined with in situ techniques,isotope labeling and size control,the detailed reaction mechanisms,the precise 2D structure-activity relationships and the rate-determining steps were revealed at a molecular level.Furthermore,the outlook of model carbon catalysis has also been proposed in this work.

Recent advances and perspectives of zinc metal-free anodes for zinc ion batteries

Zinc-ion batteries(ZIBs) are recognized as potential energy storage devices due to their advantages of low cost, high energy density, and environmental friendliness. However, zinc anodes are subject to unavoidable zinc dendrites, passivation, corrosion, and hydrogen evolution reactions during the charging and discharging of batteries, becoming obstacles to the practical application of ZIBs. Appropriate zinc metal-free anodes provide a higher working potential than metallic zinc anodes, effectively solving the problems of zinc dendrites, hydrogen evolution, and side reactions during the operation of metallic zinc anodes. The improvement in the safety and cycle life of batteries creates conditions for further commercialization of ZIBs. Therefore, this work systematically introduces the research progress of zinc metal-free anodes in “rocking chair” ZIBs. Zinc metal-free anodes are mainly discussed in four categories: transition metal oxides,transition metal sulfides, MXene(two dimensional transition metal carbide) composites, and organic compounds, with discussions on their properties and zinc storage mechanisms. Finally, the outlook for the development of zinc metal-free anodes is proposed. This paper is expected to provide a reference for the further promotion of commercial rechargeable ZIBs.

A novel metal-free porous covalent organic polymer for efficient room-temperature photocatalytic CO_(2) reduction via dry-reforming of methane

At room temperature,the conversion of greenhouse gases into valuable chemicals using metal-free catalysts for dry reforming of methane(DRM) is quite promising and challenging.Herein,we developed a novel covalent organic porous polymer (TPE-COP) with rapid charge separation of the electron–hole pairs for DRM driven by visible light at room temperature,which can efficiently generate syngas (CO and H_(2)).Both electron donor (tris(4-aminophenyl)amine,TAPA) and acceptor (4,4',4'',4'''-((1 E,1'E,1''E,1'''E)-(ethene-1,1,2,2-tetrayltetrakis (benzene-4,1-diyl))tetrakis (ethene-2,1-diyl))tetrakis (1-(4-formylbenzyl)quinolin-1-ium),TPE-CHO) were existed in TPE-COP,in which the push–pull effect between them promoted the separation of photogenerated electron–hole,thus greatly improving the photocatalytic activity.Density functional theory (DFT) simulation results show that TPE-COP can form charge-separating species under light irradiation,leading to electrons accumulation in TPE-CHO unit and holes in TAPA,and thus efficiently initiating DRM.After 20 h illumination,the photocatalytic results show that the yields reach 1123.6 and 30.8μmol g^(-1)for CO and H_(2),respectively,which are significantly higher than those of TPE-CHO small molecules.This excellent result is mainly due to the increase of specific surface area,the enhancement of light absorption capacity,and the improvement of photoelectron-generating efficiency after the formation of COP.Overall,this work contributes to understanding the advantages of COP materials for photocatalysis and fundamentally pushes metal-free catalysts into the door of DRM field.

Metal-Free 2D/2D van der Waals Heterojunction Based on Covalent Organic Frameworks for Highly Efficient Solar Energy Catalysis

Covalent organic frameworks(COFs)have emerged as a kind of rising star materials in photocatalysis.However,their photocatalytic activities are restricted by the high photogenerated electron-hole pairs recombination rate.Herein,a novel metal-free 2D/2D van der Waals heterojunction,composed of a two-dimensional(2D)COF with ketoenamine linkage(TpPa-1-COF)and 2D defective hexagonal boron nitride(h-BN),is successfully constructed through in situ solvothermal method.Benefitting from the presence of VDW heterojunction,larger contact area and intimate electronic coupling can be formed between the interface of TpPa-1-COF and defective h-BN,which make contributions to promoting charge car-riers separation.The introduced defects can also endow the h-BN with porous structure,thus providing more reactive sites.Moreover,the TpPa-1-COF will undergo a structural transformation after being integrated with defective h-BN,which can enlarge the gap between the conduction band position of the h-BN and TpPa-1-COF,and suppress electron backflow,corroborated by experimental and density functional theory calculations results.Accordingly,the resulting porous h-BN/TpPa-1-COF metal-free VDW heterojunction displays out-standing solar energy catalytic activity for water splitting without co-catalysts,and the H_(2) evolution rate can reach up to 3.15 mmol g^(−1) h^(−1),which is about 67 times greater than that of pristine TpPa-1-COF,also surpassing that of state-of-the-art metal-free-based photocatalysts reported to date.In particular,it is the first work for constructing COFs-based heterojunctions with the help of h-BN,which may provide new avenue for designing highly efficient metal-free-based photocatalysts for H_(2) evolution.

Recent advances in metal-free catalysts for the synthesis of cyclic carbonates from CO_2 and epoxides

The aim of ＂green chemistry＂ and ＂atom economy＂ is to utilize carbon dioxide and replace harmful reactants such as CO and phosgene for the production of cyclic carbonates. In this paper, metal-free catalysts including organic bases, ionic liquids, supported catalysts, organic copolymers and carbon materials for the synthesis of cyclic carbonates by the cycloaddition of carbon dioxide to epoxides are reviewed. Recent advances in the design of the catalysts and the understanding of the reaction mechanism are summarized and discussed. The synergistic effects of organic bases and hydrogen bond donors, organic bases and nucleophilic anions, hydrogen bond donors and nucleophilic anions and active components and supports are highlighted. The challenge is to develop metal-free catalysts suitable for carbon dioxide capture and fixation. The ultimate goal is to synthesize cyclic carbonates in a flow reactor directly using carbon dioxide from industrial flue gas at ambient temperature and atmospheric pressure. By using synergetic effects, a multi-functional approach can meet the design strategy of metal-free catalysts for carbon dioxide adsorption and activation as well as epoxide ring opening.

Rational design of carbon-based metal-free catalysts for electrochemical carbon dioxide reduction: A review

Electrochemical CO2 reduction to chemicals or fuels presents one of the most promising strategies for managing the global carbon balance, which yet poses a significant challenge due to lack of efficient and durable electrocatalyst as well as the understanding of the CO2 reduction reaction(CO2RR) mechanism.Benefiting from the large surface area, high electrical conductivity, and tunable structure, carbon-based metal-free materials(CMs) have been extensively studied as cost-effective electrocatalysts for CO2RR.The development of CMs with low cost, high activity and durability for CO2RR has been considered as one of the most active and competitive directions in electrochemistry and material science.In this review article,some up-to-date strategies in improving the CO2RR performance on CMs are summarized.Specifically, the approaches to optimize the adsorption of CO2RR intermediates, such as tuning the physical and electronic structure are introduced, which can enhance the electrocatalytic activity of CMs effectively.Finally, some design strategies are proposed to prepare CMs with high activity and selectivity for CO2RR.

Ordered macroporous boron phosphate crystals as metal-free catalysts for the oxidative dehydrogenation of propane

Ordered macroporous materials with rapid mass transport and enhanced active site accessibility are essential for achieving improved catalytic activity.In this study,boron phosphate crystals with a three-dimensionally interconnected ordered macroporous structure and a robust framework were fabricated and used as stable and selective catalysts in the oxidative dehydrogenation(ODH)of propane.Due to the improved mass diffusion and higher number of exposed active sites in the ordered macroporous structure,the catalyst exhibited a remarkable olefin productivity of^16 golefin gcat^-1 h^-1,which is up to 2–100 times higher than that of ODH catalysts reported to date.The selectivity for olefins was 91.5%(propene:82.5%,ethene:9.0%)at 515℃,with a propane conversion of 14.3%.At the same time,the selectivity for the unwanted deep-oxidized CO2 product remained less than 1.0%.The tri-coordinated surface boron species were identified as the active catalytic sites for the ODH of propane.This study provides a route for preparing a new type of metal-free catalyst with stable structure against oxidation and remarkable catalytic activity,which may represent a potential candidate to promote the industrialization of the ODH process.

Mesoporous carbons as metal-free catalysts for propane dehydrogenation: Effect of the pore structure and surface property

Nanocarbon materials have been used as important metal-free catalysts for various reactions including alkane dehydrogenation.However,clarifying the active sites and tuning the nanocarbon structure for direct dehydrogenation have always been significantly challenging owing to the lack of fundamental understanding of the structure and surface properties of carbon materials.Herein,mesoporous carbon materials with different pore ordering and surface properties were synthesized through a soft-templating method with different formaldehyde/resorcinol ratios and carbonization temperatures and used for catalytic dehydrogenation of propane to propylene.The highly ordered mesoporous carbons were found to have higher catalytic activities than disordered and ordered mesoporous carbons,mainly because the highly ordered mesopores favor mass transportation and provide more accessible active sites.Furthermore,mesoporous carbons can provide a large amount of surface active sites owing to their high surface areas,which is favorable for propane dehydrogenation reaction.To control the surface oxygenated functional groups,highly ordered mesoporous carbons were carbonized at different temperatures(600,700,and 800℃).The propylene formation rates exhibit an excellent linear relationship with the number of ketonic C=O groups,suggesting that C=O groups are the most possible active sites.

Surface/interface engineering of high-efficiency noble metal-free electrocatalysts for energy-related electrochemical reactions

To date,much efforts have been devoted to the high-efficiency noble metal-free electrocatalysts for hydrogen-and oxygen-involving energy conversion reactions,due to their abundance,low cost and nultifunctionally.Surface/interface engineering is found to be effective in achieving novel physicochemical properties and synergistic effects in nanomaterials for electrocatalysis.Among various engineering strategies,heteroatom-doping has been regarded as a most promising method to improve the electrocatalytic performance via the regulation of electronic structure of catalysts,and numerous works were reported on the synthesis method and mechanism investigation of heteroatom-doping electrocatalysts,though the heteroatom-doping can only provide limited active sites.Engineering of other defects such as vacancies and edge sites and construction of heterostructure have shown to open up a potential avenue for the development of noble metal-free electrocatalysts.In addition,surface functionalization can attach various molecules onto the surface of materials to easily modify their physical or chemical properties,being as a promising complement or substitute for offering materials with catalytic properties.This paper gives the insights into the diverse strategies of surface/interface engineering of the highefficiency noble metal-free electrocatalysts for energy-related electrochemical reactions.The significant advances are summarized.The unique advantages and mechanisms for specific applications are highlighted.The current challenges and outlook of this growing field are also discussed.

Design of p-n homojunctions in metal-free carbon nitride photocatalyst for overall water splitting

Two-dimensional(2D)carbon nitride(CN)photocatalysts are attracting extensive attention owing to their excellent photocatalytic properties.In this study,we successfully prepared CN materials with heterogeneous structures via hydrothermal treatment,high-temperature roasting,ball milling,sintering,and other processes.Benefitting from interface interactions in hybrid architectures,the CN photocatalysts exhibited high photocatalytic activity.The rate of hydrogen production using these CN photocatalysts reached 17028.82μmol h^(−1)g^(−1),and the apparent quantum efficiency was 11.2%at 420 nm.The ns-level time-resolved photoluminescence(PL)spectra provided information about the time-averaged lifetime of fluorescence charge carriers;the lifetime of the charge carriers causing the fluorescence of CN reached 9.99 ns.Significantly,the CN photocatalysts displayed satisfactory results in overall water splitting without the addition of sacrificial agents.The average hydrogen and oxygen production rates were 270.95μmol h^(−1)g^(−1)and 115.21μmol h^(−1)g^(−1)in 7 h,respectively,which were promising results for the applications of the catalysts in overall water splitting processes.We investigated the high efficiency of the prepared CN photocatalysts via a series of tests(UV-vis diffuse reflectance spectroscopy,photocurrent response measurements,PL emission spectroscopy,time-resolved PL spectroscopy,and Brunauer-Emmett-Teller analysis).Furthermore,the Mott-Schottky plot and current-voltage curve were acquired via electrochemical tests.The fabricated CN photocatalyst had a small p-n junction in its heterogeneous structure,which further enhanced its photocatalytic efficiency.Therefore,this work can promote the development of CN photocatalysts.

Hexagonal boron nitride:A metal-free catalyst for deep oxidative desulfurization of fuel oils

Oxidative desulfurization(ODS)has been proved to be an efficient strategy for the production of clean fuel oil.Numerous metal-based materials have been employed as excellent ODS catalysts,but being hindered by their high-cost and potential secondary pollution.In this work,we employed graphene analogous hexagonal boron nitride(h-BN)as a metal-free catalyst for ODS with hydrogen peroxide(H2O2)as the oxidant.The h-BN catalyst was characterized and proved to be a few-layered structure with relatively high specific surface areas.The h-BN catalyst showed a 99.4%of sulfur removal in fuel oil under the optimized reaction conditions.Besides,the h-BN can be recycled for 8 times without significant decrease in the catalytic performance.Detailed mechanism analysis found that it is the boron radicals in h-BN activated H2O2 to generate·OH species,which can readily oxidize sulfides to corresponding sulfones for separation.This work would provide another choice in choosing metal-free catalysts for ODS.

Direct Growth of Graphene on Silicon by Metal-Free Chemical Vapor Deposition

The metal-free synthesis of graphene on singlecrystal silicon substrates, the most common commercial semiconductor, is of paramount significance for many technological applications. In this work, we report the growth of graphene directly on an upside-down placed,single-crystal silicon substrate using metal-free, ambientpressure chemical vapor deposition. By controlling the growth temperature, in-plane propagation, edge-propagation, and core-propagation, the process of graphene growth on silicon can be identified. This process produces atomically flat monolayer or bilayer graphene domains, concave bilayer graphene domains, and bulging few-layer graphene domains. This work would be a significant step toward the synthesis of large-area and layer-controlled, high-quality graphene on single-crystal silicon substrates.

Metal-free carbocatalysis for electrochemical oxygen reduction reaction: Activity origin and mechanism

Although scientists have conducted long-term and extensive studies on oxygen reduction reaction(ORR)catalyzed by metal-free carbon materials,they mainly have focused on the preparation and properties of various doped carbon materials.There is still a lack of systematic scientific guidance on the relationship between the surface structure regulation and activity of carbon-based catalysts.In this review,some of electrochemical and computational fundamental concepts about ORR are concisely summarized.The effects of edge defect and nonmetallic doping of carbon materials on ORR behavior and mechanism have been reviewed,and activity origin identification and intermediate conversion mechanism have been discussed.The outlooks for future researches on metal-free ORR electrocatalysis are suggested.

Nanocarbon-based metal-free and non-precious metal bifunctional electrocatalysts for oxygen reduction and oxygen evolution reactions

The oxygen reduction/evolution reactions(ORR/OER) are a key electrode process in the development of electrochemical energy conversion and storage devices,such as metal-air batteries and reversible fuel cells.The search for low-cost high-performance nanocarbon-based metal-free and non-precious metal bifunctional electrocatalysts for ORR/OER alternatives to the widely-used noble metal-based catalysts is a research focus.This review aims to outline the opportunities and available options for these nanocarbon-based bifunctional electrocatalysts.Through discussion of some current scientific issues,we summarize the development and breakthroughs of these electrocatalysts.Then we provide our perspectives on these issues and suggestions for some areas in the further work.We hope that this review can improve the interest in nanocarbon-based metal-free and non-precious metal bifunctional electrocatalysts for ORR/OER.

Hydrogenated Graphene as Metal-free Catalyst for Fenton-like Reaction

Carbonaceous catalysts are potential alternatives to metal catalysts. Graphene has been paid much attention for its high surface area and light weight. Here, hydrogenated graphene has been prepared by a simple gamma ray irradiation of graphene oxide aqueous suspension at room temperature. Transmission electron microscopic, element analysis, X-ray photoelectron spectroscopy, and UV-Vis spectrophotometer studies verified the hydrogenation of graphene. The as-prepared hydrogenated graphene can be used as a metal-free carbonaceous catalyst for the Fenton-like degradation of organic dye in water.

Ten years of carbon-based metal-free electrocatalysts

Since the discovery of the first carbon-based metal-free electrocatalysts(C-MFECs,i.e.,N-doped carbon nanotubes)for the oxygen reduction reaction in 2009,the field of C-MFECs has grown enormously over the last 10 years.C-MFECs,as alternatives to nonprecious transition metals and/or precious noble metal-based electrocatalysts,have been consistently demonstrated as efficient catalysts for oxygen reduction,oxygen evolution,hydrogen evolution,carbon dioxide reduction,nitrogen reduction,and many other(electro-)chemical reactions.Recent research and development of C-MFECs have indicated their potential applications in fuel cells,metal-air batteries,and hydrogen generation through water oxidation as well as electrochemical production of various commodity chemicals,such as ammonia,alcohols,hydrogen peroxide,and other useful hydrocarbons.Further research and development of C-MFECs would surely revolutionize traditional energy conversion and storage technologies with minimal environmental impact.In this short review article,we summarize the journey of C-MFECs over the past 10 years with an emphasis on materials development and their structure-property characterization for applications in fuel cells and metal-air batteries.Current challenges and future prospects of this emerging field are also discussed.

Purified oxygenand nitrogen-modified multi-walled carbon nanotubes as metal-free catalysts for selective olefin hydrogenation

Oxygen and nitrogen-functionalized carbon nanotubes （OCNTs and NCNTs） were applied as metal-free catalysts in selective olefin hydro- genation. A series of NCNTs was synthesized by NH3 post-treatment of OCNTs. Temperature-programmed desorption, N2 physisorption, Raman spectroscopy, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy were employed to characterize the surface properties of OCNTs and NCNTs, aiming at a detailed analysis of the type and amount of oxygen- and nitrogen-containing groups as well as surface defects. The gas-phase treatments applied for oxygen and nitrogen functionalization at elevated temperatures up to 600 ℃ led to the increase of surface defects, but did not cause structural damages in the bulk. NCNTs showed a clearly higher activity than the pristine CNTs and OCNTs in the hydrogenation of 1,5-cyclooctadiene, and also the selectivity to cyclooctene was higher. The favorable catalytic properties are ascribed to the nitrogen-containing surface functional groups as well as surface defects related to nitrogen species. In contrast, oxygen-containing surface groups and the surface defects caused by oxygen species did not show clear contribution to the hydrogenation catalysis.

Recent progress of carbon-based metal-free materials in thermal-driven catalysis

The carbon-based metal-free materials as catalysts(named as carbocatalysts) have been attracting tremendous attentions in electric-,solar-and thermal-driven reactions nowadays.Compared to electrocatalysis and photocatalysis,the thermal-driven catalysis(thermocatalysis) including liquid phase and gas phase reactions involves wider scope and is relatively easy to realize practical large-scale applications.Over the past several years,some striking achievements on the design of new carbon-based metal-free materials with well-defined structures and heteroatom groups as well as the revelation of new reaction mechanisms and active sites in thermocatalysis have been obtained.However,comparative discussions regarding these recent achievements have been rarely highlighted.In this review,we systematically summarize and discuss six kinds of carbocatalysts and their applications in thermocatalysis.These materials include typical oxygen-attached carbon,surface modified carbon(graft with certain organic compounds),mono-doped carbon,co-doped carbon,carbon nitride and materials with carbon as dopant.Some new reaction processes as well as the related reaction mechanisms,active sites and intermediates are reviewed critically.Moreover,an outlook on the in-depth investigation of the metalfree carbocatalysis in the future is provided.

Nitrogen-Doped Graphene Foam as a Metal-Free Catalyst for Reduction Reactions under a High Gravity Field

Herein,we report on the effect of a high gravity field on metal-free catalytic reduction,taking the nitrobenzene(NB)reduction and methylene blue(MB)degradation as model reactions in a highgravity rotating tube reactor packed with three-dimensional(3D)nitrogen-doped graphene foam(NGF)as a metal-free catalyst.The apparent rate constant(kapp)of the metal-free catalytic reduction of NB in the rotating tube reactor under a high gravity level of 6484g(g=9.81 m s-2)was six times greater than that in a conventional stirred reactor(STR)under gravity.Computational fluid dynamics(CFD)simulations indicated that the improvement of the catalytic efficiency was attributed to the much higher turbulent kinetic energy and faster surface renewal rate in the high-gravity tube reactor in comparison w让h those in a conventional STR.The structure of the 3D metal-free catalysts was stable during the reaction process under a high gravity field,as confirmed by X-ray photoelectron spectroscopy(XPS)and Raman spectra.In the other model reaction,the rate of MB degradation also increased as the high gravity level in creased gradually,which aligns with the result for the NB catalytic reduction system.These results demonstrate the potential to use a high-gravity rotating packed tube reactor for the process intensification of metal-free catalytic reduction reactions.

Preparation and Microscopic Characterization of Asphalt Modified by Ethylene Metal-free Phthalocyanine-dispersed Graphene

Graphene-modified asphalt(GMA)for road application was prepared via using metal-free phthalocyanine-dispersed to modify an SK-70#base asphalt with graphene.The preparation parameters are as follows:the content of graphene is 0.26%based on the mass percentage of absolute ethanol,the content of nonmetal phthalocyanine is 190%based on the mass percentage of graphene,and then the GMA is prepared via unique high-speed shearing with continuing to ventilate nitrogen,which can prevent the aging of modified asphalt in the high-speed shearing process,and effectively evaluate the modifier.The penetration,softening point,force ductility,and fracture energy of GMA were significantly improved based on the base asphalt.Thus,the incorporation of graphene could enhance the base asphalt’s high-and low-temperature stability.The modification mechanism was researched via metallographic microscopy,computed tomography(CT),Fourier transform infrared spectroscopy(FTIR),and atomic force microscopy(AFM).Adsorption and physical dispersion of the asphaltenes and resins in the phthalocyanine-graphene system were confirmed.