Engineering g-C_(3)N_(4)based materials for advanced photocatalysis:Recent advances

Photocatalysis driven by abundant yet intermittent solar energy has considerable potential in renewable energy generation and environmental remediation.The outstanding electronic structure and physicochemical properties of graphitic carbon nitride(g-C_(3)N_(4)),together with unique metal-free characteristic,make them ideal candidates for advanced photocatalysts construction.This review summarizes the up-to-date advances on g-C_(3)N_(4)based photocatalysts from ingenious-design strategies and diversified photocatalytic applications.Notably,the advantages,fabrication methods and limitations of each design strategy are systemically analyzed.In order to deeply comprehend the inner connection of theory–structure–performance upon g-C_(3)N_(4)based photocatalysts,structure/composition designs,corresponding photocatalytic activities and reaction mechanisms are jointly discussed,associated with introducing their photocatalytic applications toward water splitting,carbon dioxide/nitrogen reduction and pollutants degradation,etc.Finally,the current challenges and future perspectives for g-C_(3)N_(4)based materials for photocatalysis are briefly proposed.These design strategies and limitations are also instructive for constructing g-C_(3)N_(4) based materials in other energy and environment-related applications.

Optimized electrochemical ammonia production:From metal-N_(2)/NO_(x) batteries to aqueous metal-NO_(x)^(–) batteries

Ammonia plays a crucial role in contemporary society,impacting medicine,agriculture,and the chemical industry.The conventional industrial synthesis of NH_(3) through the Haber-Bosch technique,carried out under severe reaction conditions,leads to substantial energy consumption and environmental pollution.It is thus imperative for NH_(3) synthesis methods to be investigated under more favorable conditions.Synthesis of ammonia by electrocatalysis can effectively reduce the environmental damage and other urgent problems,which is a promising solution.Metal-nitrogen series batteries(M-N batteries),such as metal-nitrogen gas batteries,metal-nitrogen oxide batteries and metal-oxynitride batteries have been regarded recently as an exemplar of concurrent NH_(3) synthesis and energy production.Nonetheless,the large-scale application of these batteries is still limited by numerous challenges are currently existing in building high-efficiency M-N batteries,including poor Faradic efficiency and low NH_(3) yield.Therefore,a comprehensive overview of M-N batteries is offered,specifically focusing on advanced strategies for designing highly efficient cathode catalysts in anticipation of future developments.The metal anodes,cathodic electro-reduction reactions,and design principles are encompassed in the discussion,offering detailed insights to enhance understanding.Mechanisms,feasibility analyses,technoeconomic assessments,device combinations,and comparative evaluations are delved into in the review,contributing to a thorough comprehension of diverse systems and their application potential.Perspectives and opportunities for future research directions are also delineated.

Heteroatom-Induced Accelerated Kinetics on Nickel Selenide for Highly Efficient Hydrazine-Assisted Water Splitting and Zn-Hydrazine Battery

Hydrazine-assisted water electrolysis is a promising energy conversion technology for highly efficient hydrogen production.Rational design of bifunctional electrocatalysts,which can simultaneously accelerate hydrogen evolution reaction(HER)/hydrazine oxidation reaction(HzOR)kinetics,is the key step.Herein,we demonstrate the development of ultrathin P/Fe co-doped NiSe_(2) nanosheets supported on modified Ni foam(P/Fe-NiSe_(2)) synthesized through a facile electrodeposition process and subsequent heat treatment.Based on electrochemical measurements,characterizations,and density functional theory calculations,a favorable“2+2”reaction mechanism with a two-step HER process and a two-step HzOR step was fully proved and the specific effect of P doping on HzOR kinetics was investigated.P/Fe-NiSe_(2) thus yields an impressive electrocatalytic performance,delivering a high current density of 100 mA cm^(−2) with potentials of−168 and 200 mV for HER and HzOR,respectively.Additionally,P/Fe-NiSe_(2) can work efficiently for hydrazine-assisted water electrolysis and Zn-Hydrazine(Zn-Hz)battery,making it promising for practical application.

COF-derived Co nanoparticles@N-doped carbon electrocatalysts for high performance Zn-air batteries

Precise modulation of the structure and composition of electrocatalysts is critical for promoting the kinetically sluggish process of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).Covalent organic frameworks(COF)offer a novel way to create highly efficient electrocatalysts due to their tunable composition,structure and surface area.Herein,we report a high-efficiency bifunctional electrocatalyst comprising Co nanoparticles embedded within N-doped carbons(Co@NCs)for Zn-air batteries(ZABs).The Co@NC is yielded via the coordination of a triazine COF with Co-containing precursors and subsequent calcination under inert atmosphere.The as-prepared Co@NC exhibits remarkable ORR/OER performance and great potential in rechargeable ZABs.The liquid ZAB constructed with Co@NC provides both high specific capacity and power density.Remarkably,the ZAB exhibits a voltage gap of 0.8 V during discharge and charge cycles and high stability for 220 h compared to the Pt/C-assembled battery.This strategy for regulating electrocatalytic activities of COF-derived carbon materials could be expanded for creating various carbon catalysts.

State-of-the-art catalysts for direct dehydrogenation of propane to propylene

With growing demand for propylene and increasing production of propane from shale gas,the technologies of propylene production,including direct dehydrogenation and oxidative dehydrogenation of propane,have drawn great attention in recent years.In particular,direct dehydrogenation of propane to propylene is regarded as one of the most promising methods of propylene production because it is an on-purpose technique that exclusively yields propylene instead of a mixture of products.In this critical review,we provide the current investigations on the heterogeneous catalysts(such as Pt,CrOx,VOx,GaOx-based catalysts,and nanocarbons)used in the direct dehydrogenation of propane to propylene.A detailed comparison and discussion of the active sites,catalytic mechanisms,influencing factors(such as the structures,dispersions,and reducibilities of the catalysts and promoters),and supports for different types of catalysts is presented.Furthermore,rational designs and preparation of high-performance catalysts for propane dehydrogenation are proposed and discussed.

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.

Nature of active phase of VO_x catalysts supported on SiBeta for direct dehydrogenation of propane to propylene

The VOx catalysts supported on dealuminated Beta zeolite(Si Beta) with varying V loadings(from 0.5 to 10 wt%) are prepared and tested for their catalytic activities in the reaction of direct dehydrogenation of propane to propylene(PDH). It is characterized that the VSi Beta catalysts possess different kinds of vanadium species on the Si Beta support, including monomeric or isolated VOx species at a low V loading, and polynuclear VOx species in different polymerization degrees at higher V loadings. The 3 VSi Beta catalyst(V loading is 3 wt%), containing isolated VOx species in monolayer, shows around 40% of propane conversion with 90% of propylene selectivity(reaction conditions: 600 o C, 4000 m L g–1 h–1) which are comparable to VSi Beta catalysts with higher V loadings. The catalytic activity exhibits a good linear relationship with the amount of generated acidic sites, which are derived from the interaction sites between VOx species and Si Beta support, and keeps stable after several regeneration cycles. Thus, as the VOx species directly contact with Si Beta support via V–O–Si bonds, a reactivity enhancement can be achieved. While, the initial valence state of V does not seem to influence the catalytic performance. Moreover, the aggregation degree of VOx species determines the propylene selectivity and deactivation rate, both of which increase as raising the V loading amount.

P-doped mesoporous carbons for high-efficiency electrocatalytic oxygen reduction

Chemically modified carbonaceous materials have attained utmost attention in the fields of renewable energy storage and conversion,due to the controllable physicochemical properties,tailorable micro-/nanostructures,and respectable stability.Herein,P-doped mesoporous carbons were synthesized by using F127 as the soft template,organophosphonic acid as the P source and phenolic resin as the carbon source.Small amounts of iron species were introduced to act as a graphitization catalyst.The synthesized carbons exhibit the well-defined wormhole-like pore structure featuring high specific surface area and homogenously doped P heteroatoms.Notably,introducing iron species during the synthesis process can optimize the textural properties and the degree of graphitization of carbon materials.The doping amount of P has an important effect on the porous structure and the defect degree,which correspondingly influence the active sites and the oxygen reduction reaction(ORR)activity.The resultant material presents superior catalytic activity for the ORR,together with remarkably enhanced durability and methanol tolerance in comparison with the commercial Platinum catalyst,demonstrating the possibility for its use in electrode materials and electronic nanodevices for metal-air batteries and fuel cells.

N-doped porous carbon hollow microspheres encapsulated with iron-based nanocomposites as advanced bifunctional catalysts for rechargeable Zn-air battery

The design and development of low-cost,efficient,and stable bifunctional electrocatalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desirable for rechargeable metal-air batteries.In this work,N-doped porous hollow carbon spheres encapsulated with ultrafine Fe/Fe3O4 nanoparticles(FeOx@N-PHCS)were fabricated by impregnation and subsequent pyrolysis,using melamine-formaldehyde resin spheres as self-sacrifice templates and polydopamine as N and C sources.The sufficient adsorption of Fe3+on the polydopamine endowed the formation of Fe-Nx species upon high-temperature carbonization.The prepared FeOx@N-PHCS has advanced features of large specific surface area,porous hollow structure,high content of N dopants,sufficient Fe-Nx species and ultrafine FeOx nanoparticles.These features endow FeOx@N-PHCS with enhanced mass transfer and considerable active sites,leading to high activity and stability in catalyzing ORR and OER in alkaline electrolyte.Furthermore,the rechargeable Zn-air battery with FeOx@N-PHCS as air cathode catalyst exhibits a large peak power density,narrow charge-discharge potential gap and robust cycling stability,demonstrating the potential of the fabricated FeOx@N-PHCS as a promising electrode material for metal-air batteries.This new finding may open an avenue for rational design of bifunctional catalysts by integrating different active components within all-in-one catalyst for different electrochemical reactions.

Phosphonate-derived nitrogen-doped cobalt phosphate/carbon nanotube hybrids as highly active oxygen reduction reaction electrocatalysts

The exploration of cost-effective non-noble-metal electrocatalysts is highly imperative to replace the state-of-the-art platinum-based catalysts for oxygen reduction reaction(ORR). Here, we prepared cobalt phosphonate-derived N-doped cobalt phosphate/carbon nanotube hybrids(Co Pi C-N/CNTs) by hydrothermal treatment of N-containing cobalt phosphonate and oxidized carbon nanotubes(o-CNT) followed by high-temperature calcination under nitrogen atmosphere. The resultant Co Pi C-N/CNT exhibits a superior electrocatalytic performance for the ORR in alkaline media, which is equal to the commercial Pt/C catalyst in the aspect of half-wave potential, onset potential and diffuse limiting current density. Furthermore, the excellent tolerance to methanol and strong durability outperform those of commercial Pt/C. It is found that cobalt phosphonate-derived N-doped cobalt phosphate and the in-situ formed graphitic carbons play key roles on the activity enhancement. Besides, introducing a suitable amount of CNTs enhances the electronic conductivity and further contributes to the improved ORR performance.

Aluminum and phosphorus codoped “superaerophobic” Co3O4 microspheres for highly efficient electrochemical water splitting and Zn-air batteries

Multifunctional non-precious catalysts for hydrogen/oxygen evolution reaction(HER/OER) and oxygen reduction reaction(ORR) constitute the bottleneck in the applications in electrochemical overall water splitting(OWS) and Zn-air batteries. Herein, a trifunctional electrocatalyst of urchin-like Al,P-codoped Co3O4 microspheres supported on Ni foam(denoted as AP-CONPs/NF) was fabricated via a hydrothermal process and subsequent low-temperature annealing and phosphorization, exhibiting enhanced OER, HER and ORR activities compared with single-doped and undoped samples. Their surface self-organized microstructure and excellent "superaerophobic" feature make a high bubble repellency, which boost diffusion of reactants and electrolyte-electrode intimate contact. The codoping of Al and P elements into Co3O4 betters right the balance among surface chemical state, the increased oxygen vacancies and the promoted charge transfer. Encouraged by these synergistic advantages, the AP-CONPs/NF was further employed as excellent bifunctional electrodes for the OWS(low cell voltage of 1.57 V at 10 mA cm-2) and as air cathode for rechargeable Zn-air batteries(high power density of 89.1 mW cm-2), which demonstrates a great feasibility for practical applications.

Fabrication strategies of porous precious-metal-free bifunctional electrocatalysts for overall water splitting:Recent advances

Electrocatalytic water splitting using power generated from renewable energy to produce hydrogen has been considered as one of the more attractive approach to alleviate the problems of energy crisis and environmental pollution.One of the biggest challenges for the large-scale application of water electrolysis is the searching of the low cost electrocatalysts with high and stable activity toward both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).The well-developed porous features of materials synthesized from the earth abundant elements endow them with the enhanced mass transfer and improved electronic interconnection during electrochemical reactions,resulting in the excellent electrocatalytic performance for both OER and HER.Herein,this review focuses on the recent development of innovation strategies for the fabrication of porous non-noble-metal materials including heteroatom-doped carbon-based and transition metal(mainly Co,Ni,and Fe)-based materials as efficient electrocatalysts for overall water splitting.Specially,a detailed discussion of the structure–activity correlation gives an insight on the origin of the high electrocatalytic performance of porous materials obtained from different strategies,and provides guidance for future design and preparation of highly efficient electocatalysts based on non-precious carbon or metal materials for overall water splitting.

Facile synthesis of Mo2C nanoparticles on N-doped carbon nanotubes with enhanced electrocatalytic activity for hydrogen evolution and oxygen reduction reactions

Developing low-cost and highly-efficient electrocatalysts for renewable energy conversion technologies has attracted even-increasing attention. Molybdenum carbide materials have recently emerged as a type of promising catalysts for electrocatalytic reactions due to the earth-abundance and Pt-resembled electrical properties. In this work, taking the advantage of the interaction between the basic groups of the Mo(VI)-melamine polymer and the acidic groups on the surface of the oxidized carbon nanotubes(CNTs), N-doped CNTs supported Mo2C nanoparticles(Mo2C/NCNT) are prepared, which exhibit outstanding electrocatalytic activity and durability for both the hydrogen evolution and oxygen reduction reactions. The impressive performance of Mo2C/NCNT can be attributed to the small size of Mo2C particles, the large exposure ratio of surface sites and the presence of N-doped CNTs. This work enlarges the multi-field applications of molybdenum carbide-base materials as promising non-precious metal electrocatalysts, which is of great significance for sustainable energy-related technologies.

Engineering morphologies of cobalt oxide/phosphate-carbon nanohybrids for high-efficiency electrochemical water oxidation and reduction

Active non-noble metal catalysts plays a decisive role for water electrolysis,however,the rational design and development of cost-efficient electrocatalysts with Pt/IrO2-like activity is still a challenging task.Herein,a facile one-step electrodeposition route in deep eutectic solvents(DESs) is developed for morphology-controllable synthesis of cobalt oxide/phosphate-carbon nano hybrids on nickel foam(CoPO@C/NF).A series of CoPO@C/NF nanostructures including cubes,octahedrons,microspheres and nanoflowers are synthesized,which show promising electrocatalytic properties toward oxygen and hydrogen evolution reactions(OER/HER).Such surface self-organized microstructure with accessible active sites make a significant contribution to the enhanced electrochemical activity,and hybridizing cobalt oxide with cobalt pyrophosphates and carbon can result in enhanced OER performance through synergistic catalysis.Among all nanostructures,the obtained microspherical CoPO@C/NF-3 catalyst exhibits excellent catalytic activities for OER and HER in 1.0 M KOH,affording an anodic current density of 10 mA cm^(-2) at overpotentials of 293 mV for OER and 93 mV for HER,with good long-time stability.This work offers a practical route for engineering the high-performance electrocatalysts towards efficient energy conversion and storage devices.

CrOx supported on high-silica HZSM-5 for propane dehydrogenation

Industrial propane dehydrogenation(PDH)catalysts generally suffer from low catalytic stability due to the coke formation onto the catalyst surface to cover the active sites.The exploitation of an efficient catalyst with both high catalytic selectivity and long-term stability toward PDH is of great importance but challenging to make.Herein CrOx supported on high-silica HZSM-5 with a SiO2/Al2O3 ratio of 260(Cr/Z-5(260)is synthesized by a simple wet impregnation method,which exhibits high catalytic activity,good selectivity and excellent stability for PDH.At a weight hourly space velocity(WHSV)of 0.59 h-1,a propylene formation rate of 4.1 mmol g-1cath-1(~32.6% propane conversion and ~94.2% propylene selectivity)can be maintained over the 5%Cr/Z-5(260)catalyst after 50 h time on stream,which is much better than commercial Cr/Al2O3(Catofin process,catalyst life is several hours)at the same reaction conditions.With increasing the WHSV to 5.9 h-1,a high propylene formation rate of 27.9 mmol gcat-1h-1can be obtained over the 5%Cr/Z-5(260)catalyst after 50 h time on stream,demonstrating a very promising PDH catalyst.Characterization results and Na+doping experiments reveal that the Cr species combined with Br?nsted acid sites in Cr/HZSM-5 catalysts are responsible for the high catalytic performance.In particular,the Br?nsted acid sites in HZSM-5 zeolite could increase the propane adsorption and enhance the C–H bond activation.Furthermore,the high surface area and well-defined pores of HZSM-5 zeolite can provide a special environment for the dispersion and stabilization of Cr species,thus guaranteeing high catalytic activity and stability.

Insights into efficient transition metal-nitrogen/carbon oxygen reduction electrocatalysts

It is of vital importance to accelerate the sluggish oxygen reduction reaction(ORR)process at the cathode with earth-abundant metal-based catalysts for the commercialization of low-temperature polymer electrolyte membrane fuel cells.In consideration of high catalytic activity,long-term stability and low cost of potential ORR electrocatalysts,transition metal species have attracted much interest and transition metal-nitrogen-carbon(M-N/C,M=Fe,Co,Ni,Mn,etc.)catalysts have been widely considered as the most promising non-precious metal catalysts for ORR.Herein,the fundamental understanding of ORR catalytic mechanism and the identification of active centers are briefly introduced,and then different M-N/C catalysts classified by precursors with the strategies for design and optimization are highlighted.The challenges and possible opportunity for future development of high-performance ORR catalysts are finally proposed.

Facile synthesis of molybdenum carbide nanoparticles in situ decorated on nitrogen-doped porous carbons for hydrogen evolution reaction

Molybdenum-based electrocatalysts are promising candidates of platinum (Pt)-based materials in electrocatalyzing hydrogen evolution reaction (HER), due to their cost-efficient and resembled electronic properties. Reported herein is the preparation of molybdenum carbide nanoparticles uniformly decorated on nitrogen-modified carbons (Mo2C/NC) through the carbonization of Mo-based polymers under hydrogen atmosphere by using poly(p-phenylenediamine) and ammonium heptamolybdate polymer analogue as precursors. And the molybdenum nitride nanoparticles loaded on porous N-doped carbons (Mo2N/NC) are also fabricated by calcination the polymer precursors in nitrogen gas. The Mo2C/NC shows more excellent electrocatalytic activity than Mo2N/NC in 0.5 M H2SO4, together with robust long-term durability. The well-crystalline nanoparticles and the increased electron conductivity are the main characters responded for the high catalytic efficiency of the fabricated electrocatalysts. This easily fabrication procedure may provide a facile route to prepare non-noble metal carbide/nitride catalysts featuring wellengineered structural and textural peculiarities for realistic energy conversion system.

CeO_2修饰介孔TiO_2和ZrO_2负载金催化剂催化废气中CO和挥发性有机化合物降解(英文)

Mesoporous 氧化物 TiO 2 和 ZrO 2, 经由中立 C 13(EO)6–Zr(OC3 H 7)4 集会小径，和 deposition–precipitation (DP ) 准备的修改 ceria 的 TiO 2 和 ZrO 2, 方法，展示高表面区域和一致毛孔尺寸分布被用作对金催化剂的支持。支持的金催化剂为空气污染物质的催化消退被估计，即，公司， CH 3 哦，并且(CH 3)2 O。金牌被一个 DP 方法在 mesoporous 氧化物上支持。支持和催化剂被粉末 X 光检查衍射，高分辨率的传播电子显微镜学， N 2 adsorption–desorption 分析，和规划温度的减小技术描绘。在象由 ceria 的结构、催化的性质的积极修正一样的 ceria 和 mesoporous ZrO 2 和 TiO 2 之间的 synergistic 相互作用的高度被观察。ceria 添加剂与 mesoporous 氧化物交往并且在支持的 reducibility 上导致强壮的效果。催化剂的催化行为被讨论决定修改在金 nanoparticles 和 ceria-mesoporous 氧化物支持之间的添加剂和可能的相互作用的 ceria 的角色。在修改 ceria 的 mesoporous ZrO 2 上支持的金催化剂显示了优异催化活动(在 10 °C 和 CH 3 在 60 °C 的 OH ) 。高催化的活动能被归因于支持的能力帮助氧空缺形成。研究显示修改 ceria 的 mesoporous 氧化物支持作为对基于黄金的催化剂的支持有潜力。

Synergistically enhanced activity and stability of bifunctional nickel phosphide/sulfide heterointerface electrodes for direct alkaline seawater electrolysis

Direct electrolysis of seawater to generate hydrogen is an attractive but challenging renewable energy storage technology.Reasonable design of seawater electrolysis catalysts should integrate high activity for hydrogen evolution reaction(HER)/oxygen evolution reaction(OER)and enhanced physical/electrochemical stability in seawater.Herein,we demonstrate the development of a Ni foam(NF)supported interfacial heterogeneous nickel phosphide/sulfide(Ni_(2)P/NiS_(2))microsphere electrocatalyst(NiPS/NF)through a facile electrodeposition and subsequent phosphorization/sulfuration process.After NiS_(2)modification,a charge redistribution on the heterointerface is demonstrated and a more advantageous covalent nature of the Ni-P bond is obtained for more easily adsorption of H*and H_(2)O.The NiPS/NF thus yields an impressive electrocatalytic performance in 1.0 M KOH,requiring small overpotentials of 169 and 320 mV for HER and OER to obtain a high current density of 100 m A cm^(-2),respectively.The NiPS/NF can also work efficiently in alkaline seawater with negligible activity degradation,requiring overpotentials of only 188 and 344 mV for a current density of 100 m A cm^(-2)for HER and OER,respectively.A synergistically enhanced physical/electrochemical long-term stability NiPS/NF in saline water is also demonstrated.