Customization of FeNi alloy nanosheet arrays inserted with biomass-derived carbon templates for boosted electromagnetic wave absorption

Electromagnetic wave(EMW)-absorbing materials have considerable capacity in the military field and the prevention of EMW radiation from harming human health.However,obtaining lightweight,high-performance,and broadband EMW-absorbing material remains an overwhelming challenge.Creating dielectric/magnetic composites with customized structures is a strategy with great promise for the development of high-performance EMW-absorbing materials.Using layered double hydroxides as the precursors of bimetallic alloys and combining them with porous biomass-derived carbon materials is a potential way for constructing multi-interface heterostructures as efficient EMW-absorbing materials because they have synergistic losses,low costs,abundant resources,and light weights.Here,FeNi alloy nanosheet array/Lycopodium spore-derived carbon(FeNi/LSC)was prepared through a simple hydrothermal and carbonization method.FeNi/LSC presents ideal EMW-absorbing performance by benefiting from the FeNi alloy nanosheet array,sponge-like structure,capability for impedance matching,and improved dielectric/magnetic losses.As expected,FeNi/LSC exhibited the minimum reflection loss of-58.3 dB at 1.5 mm with 20wt%filler content and a widely effective absorption bandwidth of 4.92 GHz.FeNi/LSC composites with effective EMW-absorbing performance provide new insights into the customization of biomass-derived composites as high-performance and lightweight broadband EMW-absorbing materials.

Integration of pore structure modulation and B,N co-doping for enhanced capacitance deionization of biomass-derived carbon

Biomass-derived carbon has demonstrated great potentials as advanced electrode for capacitive deionization(CDI),owing to good electroconductivity,easy availability,intrinsic pores/channels.However,conventional simple pyrolysis of biomass always generates inadequate porosity with limited surface area.Moreover,biomass-derived carbon also suffers from poor wettability and single physical adsorption of ions,resulting in limited desalination performance.Herein,pore structure optimization and element co-doping are integrated on banana peels(BP)-derived carbon to construct hierarchically porous and B,N co-doped carbon with large ions-accessible surface area.A unique expansionactivation(EA)strategy is proposed to modulate the porosity and specific surface area of carbon.Furthermore,B,N co-doping could increase the ions-accessible sites with improved hydrophilicity,and promote ions adsorption.Benefitting from the synergistic effect of hierarchical porosity and B,N co-doping,the resultant electrode manifest enhanced CDI performance for NaCl with large desalination capacity(29.5 mg g^(-1)),high salt adsorption rate(6.2 mg g^(-1)min^(-1)),and versatile adsorption ability for other salts.Density functional theory reveals the enhanced deionization mechanism by pore and B,N co-doping.This work proposes a facile EA strategy for pore structure modulation of biomass-derived carbon,and demonstrates great potentials of integrating pore and heteroatoms-doping on constructing high-performance CDI electrode.

High loading FeS2 nanoparticles anchored on biomass-derived carbon tube as low cost and long cycle anode for sodium-ion batteries

In recent years, the sodium storage mechanism and performance optimization of FeS2 have been studied intensively. However, before the commercial application of FeS2, preconditions of low-cost, simple craft and scale production of nanoscale FeS2 are also essential. Based on above challenges, mesh-like FeS2/carbon tube/FeS2 composites are prepared simply from green, low-cost and renewable natural herb in this work. With the assistance of protogenetic interconnected carbon tube network(only 5.3 wt%), FeS2/carbon tube/FeS2 composites show high capacity(542.2 mA h g^-1), good stability(< 0.005% per cycle over 1000 cycles), and excellent rate performance(426.2 mA h g^-1 at 2 A g^-1).The outstanding electrochemical performance of FeS2/carbon tube/FeS2 composites may be attributed to the unique interconnected reticular structure, meaning that FeS2 nanoparticles are effectively immobilized by carbon tube network via physical encapsulation and chemical bonding.More importantly, this work may provide green and low cost preparation method for specially structured metal sulfides/carbon composites,which promotes their commercial utilization in environmentally friendly energy storage system.

Biomass-Derived Carbon Heterostructures Enable Environmentally Adaptive Wideband Electromagnetic Wave Absorbers

Although advances in wireless technologies such as miniature and wearable electronics have improved the quality of our lives,the ubiquitous use of electronics comes at the expense of increased exposure to electromagnetic(EM)radiation.Up to date,extensive efforts have been made to develop high-performance EM absorbers based on synthetic materials.However,the design of an EM absorber with both exceptional EM dissipation ability and good environmental adaptability remains a substantial challenge.Here,we report the design of a class of carbon heterostructures via hierarchical assembly of graphitized lignocellulose derived from bamboo.Specifically,the assemblies of nanofibers and nanosheets behave as a nanometer-sized antenna,which results in an enhancement of the conductive loss.In addition,we show that the composition of cellulose and lignin in the precursor significantly influences the shape of the assembly and the formation of covalent bonds,which affect the dielectric response-ability and the surface hydrophobicity(the apparent contact angle of water can reach 135°).Finally,we demonstrate that the obtained carbon heterostructure maintains its wideband EM absorption with an effective absorption frequency ranging from 12.5 to 16.7 GHz under conditions that simulate the real-world environment,including exposure to rainwater with slightly acidic/alkaline pH values.Overall,the advances reported in this work provide new design principles for the synthesis of high-performance EM absorbers that can find practical applications in real-world environments.

Biomass-Derived Carbon Dots and Their Applications

Carbon dots(CDs) have received much attention due to their superior properties including water solubility, low toxicity, biocompatibility, small size,fluorescence, and ease of modification. The use of a more environmentally friendly method to prepare high-quality CDs is still an urgent question waiting for solve. The use of renewable, inexpensive, and green biomass resources not only meets the urgent need for large-scale synthesis biomass CDs(BCDs), but also promotes the development of sustainable applications.In this article, we summarize the representative methods for synthesizing BCDs in green and simple ways using biomass as a carbon source, including hydrothermal carbonization, and microwave, pyrolysis. The prepared BCDs have a uniform particle size distribution and a relatively high throughput,which provide a method to scale up industrial production. Moreover, the integration of specific optical properties, that is, tunable photoluminescence and up-photoluminescence, has led to remarkable use in bioimaging, sensing,and drug delivery. But the current review is not particularly comprehensive for BCDs. Therefore, we now provide a review focusing on the synthesis,properties, and recent advances in BCDs in biosensing, bioimaging,optoelectronics, and catalytic applications.

Designandconstructionof athree-dimensionalelectrodewith biomass-derived carbon current collector andwater-soluble binder for high-sulfur-loading lithium-sulfur batteries

Lithium-sulfur batteries attract lots of attention due to their high specific capacity,low cost,and environmental friendliness.However,the low sulfur utilization and short cycle life extremely hinder their application.Herein,we design and fabricate a three-dimensional electrode by a simple filtration method to achieve a high-sulfur loading.Biomass porous carbon is employed as a current collector,which not only enhances the electronic transport but also effectively limits the volume expansion of the active material.Meanwhile,an optimized carboxymethyl cellulose binder is chosen.The chemical bonding restricts the shuttle effect,leading to improved electrochemical performance.Under the ultrahigh sulfur load of 28mg/cm2,the high capacity of 18mAh/cm2 is still maintained,and stable cycling performance is obtained.This study demonstrates a viable strategy to develop promising lithium-sulfur batteries with a three-dimensional electrode,which promotes sulfur loading and electrochemical performance.

Biomass-derived porous carbon with single-atomic cobalt toward high-performance aqueous zinc-sulfur batteries at room temperature

Aqueous zinc-sulfur batteries at room temperature hold great potential for next-generation energy storage technology due to their low cost,safety and high energy density.However,slow reaction kinetics and high activation energy at the sulfur cathode pose great challenges for the practical applications.Herein,biomass-derived carbon with single-atomic cobalt sites(MMPC-Co)is synthesized as the cathode in Zn-S batteries.The catalysis of single-atom Co sites greatly promotes the transform of cathode electrolyte interface(CEI)on the cathode surface,while offering accelerated charge transfer rate for high conversion reversibility and large electrochemical surface area(ECSA)for high electrocatalytic current.Furthermore,the rich pore structure not only physically limits sulfur loss,but also accelerates the transport of zinc ions.In addition,the large pore volume of MMPC-Co is able to relieve the stress effect caused by the volume expansion of Zn S during charge/discharge cycles,thereby maintaining the stability of electrode structure.Consequently,the sulfur cathode maintains a high specific capacity of 729.96 m A h g^(-1)after 500 cycles at4 A g^(-1),which is much better than most cathode materials reported in the literature.This work provides new insights into the design and development of room-temperature aqueous Zn-S batteries.

Interfacial growth of N,S-codoped mesoporous carbon onto biomass-derived carbon for superior potassium-ion storage

Carbonaceous materials have been recognized as one of the most promising anode materials for potassium-ion batteries(PIBs)due to their abundant raw materials,controllable structure,superior conductivity,and good chemical inertness.However,the large radius of K ions and the low potassium content of intercalation compounds result in the sluggish storage kinetics and low reversible capacity of carbon anodes.In this work,we present a unique heteroatom-doped carbon composite(denoted as NS-MC/SC)through a facile interfacial assembly route and simple heat-treatment process,where NS-MC is well grafted onto the biomass-derived spore carbon(SC).This unique structural design endows it with abundant mesoporous channels,expanded layer spacing,and highly doped N and S.With these merits,the NS-MC/SC anode in PIBs exhibits a high reversible capacity of 350.4 mAh·g^(-1) at 100 mA·g^(-1) after 300 cycles,and an outstanding cycling stability.Besides,in-situ Raman spectra further verify the high reversibility of K ions insertion/extraction.Importantly,theoretical simulations also reveal that the N,S dual-doping is an efficient approach for improving the potassium-ion storage performance of NS-MC/SC.

Preparation of biomass-derived carbon loaded with MnO_(2) as lithium-ion battery anode for improving its reversible capacity and cycling performance

Biomass-derived carbon materials for lithiumion batteries emerge as one of the most promising anodes from sustainable perspective.However,improving the reversible capacity and cycling performance remains a long-standing challenge.By combining the benefits of K2CO_(3) activation and KMnO_(4) hydrothermal treatment,this work proposes a two-step activation method to load MnO_(2) charge transfer onto biomass-derived carbon(KAC@MnO_(2)).Comprehensive analysis reveals that KAC@MnO_(2) has a micro-mesoporous coexistence structure and uniform surface distribution of MnO_(2),thus providing an improved electrochemical performance.Specifically,KAC@MnO_(2) exhibits an initial chargedischarge capacity of 847.3/1813.2 mAh·g^(-1) at 0.2 A·g^(-1),which is significantly higher than that of direct pyrolysis carbon and K2CO_(3) activated carbon,respectively.Furthermore,the KAC@MnO_(2) maintains a reversible capacity of 652.6 mAh·g^(-1) after 100 cycles.Even at a high current density of 1.0 A·g^(-1),KAC@MnO_(2) still exhibits excellent long-term cycling stability and maintains a stable reversible capacity of 306.7 mAh·g^(-1) after 500 cycles.Compared with reported biochar anode materials,the KAC@MnO_(2) prepared in this work shows superior reversible capacity and cycling performance.Additionally,the Li+insertion and de-insertion mechanisms are verified by ex situ X-ray diffraction analysis during the chargedischarge process,helping us better understand the energy storage mechanism of KAC@MnO_(2).

State-of-the-art of biomass-derived carbon dots: Preparation, properties, and applications

Carbon dots (CDs) have attracted considerable attention as a new type of fluorescent carbon nanomaterial because of their excellent optical properties, biocompatibility, and high electrical conductivity. Research on CDs has been conducted for nearly two decades and has focused on numerous precursors, various synthesis conditions and properties and applications of CDs. Biomass is critical in the green development of CDs because of its low cost, environmental friendliness, and sustainable properties. This review focuses on the advantages and applications of biomass-derived CDs. In addition, the challenges of photobleaching, toxicity, and stability of biomass-based CDs are discussed in detail. Lastly, the prospects and challenges of biomass-derived CDs are highlighted.

A thermodynamic view on the in-situ carbon dioxide reduction by biomass-derived hydrogen during calcium carbonate decomposition

In the carbonate industry,deep decarbonization strategies are necessary to effectively remediate CO_(2).These strategies mainly include both sustainable energy supplies and the conversion of CO_(2)in downstream processes.This study developed a coupled process of biomass chemical looping H2 production and reductive calcination of CaCO_(3).Firstly,a mass and energy balance of the coupled process was established in Aspen Plus.Following this,process optimization and energy integration were implemented to provide optimized operation conditions.Lastly,a life cycle assessment was carried out to assess the carbon footprint of the coupled process.Results reveal that the decomposition temperature of CaCO_(3)in an H_(2)atmosphere can be reduced to 780℃(generally around 900℃),and the conversion of CO_(2)from CaCO_(3)decomposition reached 81.33%with an H2:CO ratio of 2.49 in gaseous products.By optimizing systemic energy through heat integration,an energy efficiency of 86.30%was achieved.Additionally,the carbon footprint analysis revealed that the process with energy integration had a low global warming potential(GWP)of-2.624 kg·kg^(-1)(CO_(2)/CaO).Conclusively,this work performed a systematic analysis of introducing biomass-derived H_(2)into CaCO_(3)calcination and demonstrated the positive role of reductive calcination using green H_(2)in mitigating CO_(2)emissions within the carbonate industry.

Recent progress of transition metal-based biomass-derived carbon composites for supercapacitor

Supercapacitors(SCs)have been considered as the most promising energy storage device due to high power density,long cycle life,and fast energy storage and efficient delivery.The excellent electrode materials of SCs generally have based on large porous structure,excellent conductivity,and heteroatom doping for charge transfer.Among various electrode materials,biomass-derived carbon materials have received widespread attention owing to excellent performances,environmental friendliness,lowcost and renewability.Additionally,composites materials based on biomass-derived carbon and transition metalbased material can obtain more advantages of structural and performance than single component,which opens up a new way for the fabrication of high-performance SC electrode materials.Therefore,this review aims to the recent progress on the design and fabrication of biomassderived carbons/transition metal-based composites in supercapacitor application.Finally,the development trends and challenges of biomass-derived electrode materials have been discussed and prospected.

In-situ growth of ZnS/FeS heterojunctions on biomass-derived porous carbon for efficient oxygen reduction reaction

It is an urgent task to develop highly efficient non-noble metal electrocatalysts in the direction of ORR,but still a huge and long-term challenge.Herein,an efficient one-step pyrolysis of Sichuan pepper powder,2,2-bipyridine,FeCl3,Na SCN,and ZnCl2 at 900℃ provides the FeS/ZnS@N,S-C-900 hybrid catalyst.Transmission electron microscopy(TEM)images and Mott-Schottky curves clearly reveal the in-situ constructed abundant FeS/ZnS-based p-n junctions dispersed on the biomass-derived porous carbon surface of FeS/ZnS@N,S-C-900.The as-prepared FeS/ZnS@N,S-C-900 hybrid exhibits superior ORR performance in comparison with Pt/C in 0.1 M KOH with high onset(Eonset)and half-wave potentials(E1/2)of 1.00 and 0.880 V vs.RHE,large limiting current density(JL)of 5.60 mA cm-2,and robust durability and methanol tolerance.Impressively,upon the light irradiation,FeS/ZnS@N,S-C-900 produces a photocurrent as high as ca.0.3μA cm-2,resulting in further improvement over Eonset,E1/2,and JLof FeS/ZnS@N,S-C-900 to1.10 V vs.RHE,0.885 V vs.RHE,and 6.02 mA cm-2.Experiment in combination with theoretical calculations demonstrate the significant effect of FeS/ZnS heterojunction on the enhanced ORR catalytic activity of FeS/ZnS@N,S-C-900.This work is useful for the development of advanced heterojunction-based ORR catalysts for various energy conversion devices.

Renewable biomass-derived carbons for electrochemical capacitor applications

Biomass is rich,renewable,sustainable,and green resources,thereby excellent raw material for the fabrication of carbon materials.The diversity in structure and morphology of biomass are relevant in obtaining carbon materials with dif-ferent structures and performances.The inherent ordered porous structure of biomass also benefits the activation process to yield porous carbons with ultra-high specific surface area and pore volume.Besides,obtained biomass-derived carbons(BDCs)are hard carbon with porous morphology,stable structure,supe-rior hardness/strength,and good cycling performances when used in electro-chemical capacitors(ECs).The inherent N,S,P,and O elements in biomass yield naturally self-doped N,S,P,and O BDCs with unique intrinsic structures.In this paper,the synthesis approaches and applications of BDCs in ECs are reviewed.It shows that BDCs electrochemical performances are highly determined by their pore structures,specific surface areas,heteroatoms doping,graphitization degree,defects,and morphologies.The electrochemical performances of BDCs can further be improved by compositing with other materials,such as graphene,carbon nanofibers/nanotubes,transition metal oxides or hydroxides,and con-ducting polymers.The future challenges and outlooks of BDCs are also provided.

Biomass-derived porous carbon materials for advanced lithium sulfur batteries

Biomass, as the most widely used carbon sources, is the main ingredient in the formation of fossil fuels. Biomass-derived novel carbons(BDNCs) have attracted much attention because of its adjustable physical/chemical properties, environmentally friendliness, and considerable economic value. Nature contributes to the biomass with bizarre microstructures with micropores, mesopores or hierarchical pores.Currently, it has been confirmed that biomass has great potential applications in energy storage devices,especially in lithium-sulfur(Li–S) batteries. In this article, the synthesis and function of BDNCs for Li–S batteries are presented, and the electrochemical effects of structural diversity, porosity and surface heteroatom doping of the carbons in Li-S batteries are discussed. In addition, the economic benefits, new trends and challenges are also proposed for further design excellent BDNCs for Li–S batteries.

Biomass-derived nitrogen-doped hierarchical porous carbon as efficient sulfur host for lithium–sulfur batteries

Lithium-sulfur(Li-S) battery is a potential energy storage technology with high energy density and low cost. However, the gap between theoretical expectation and practical performance limits its wide implementation. Herein, we report a nitrogen-doped porous carbon derived from biomass pomelo peel as sulfur host material for Li-S batteries. The hierarchical porous architecture and the polar surface introduced by N-doping render a favorable combination of physical and chemical sulfur confinements as well as an expedite electron/ion transfer, thus contributing to a facilitated and stabilized sulfur electrochemistry. As a result, the corresponding sulfur composite electrodes exhibit an ultrahigh initial capacity of 1534.6 mAh g^-1, high coulombic efficiency over 98% upon 300 cycles, and decent rate capability up to 2 C. This work provides an economical and effective strategy for the fabrication of advanced carbonaceous sulfur host material as well as the significant improvement of Li-S battery performance.

Biomass-derived Porous Carbon Materials for Supercapacitor Electrodes:A Review

The development of renewable,cost-efficient,and environmentally friendly electrode materials with excellent performance is urgently needed for improving supercapacitors(SCs).Recently,biomass-derived porous carbons(BPCs)have received increasing attention due to their excellent physical and chemical properties,widespread availability,and low production cost.In this review,the progress in preparing BPCs and the properties of prepared BPCs are presented and discussed.In addition,the applications of BPCs as electrode materials for supercapacitors are also summarized.More importantly,the pore structure and surface properties of BPCs are all determining factors to improve electrochemical performance.Moreover,a high energy density and power density can be pursued by using composites based on BPCs as electrode materials,of which combining transition metallic oxide with BPCs is one of the most attractive selections.Therefore,rational design of BPCs with respect to the supercapacitor's performance should be conducted in the future.

Biomass-derived porous carbon highly efficient for removal of Pb(Ⅱ) and Cd(Ⅱ)

The utilization of abundant and renewable biomass to fabricate advanced functional materials is considered a promising route for environmental applications.Herein,Lignin-based porous carbon with layered graphene-like structure(LPC)is successfully synthesized and applied to efficiently remove Pb(Ⅱ)and Cd(Ⅱ).The as-synthesized LPC materials are systematically characterized and these results show that LPC has a porous graphene-like structure,facilitating the diffusion and immobilization of heavy metal ions.The influence of different reaction parameters(solution pH,initial concentration of metal ions,contact time and adsorbent amount)on the adsorption performance is investigated in details.The results demonstrate that LPC can achieve superior adsorption capacities of 250.5 mg·g^-1 for Pb(Ⅱ)and 126.4 mg·g^-1 for Cd(Ⅱ),which are far superior to the previously reported adsorbents.Pseudo-second order kinetics model and Freundlich isotherm model describe the adsorption process well.Furthermore,the exhausted LPC can be regenerated easily and exhibits the removal efficiency of 96%and 92%for Pb(Ⅱ)and Cd(Ⅱ)after five continuous runs,respectively.This study shows a sustainable strategy for the design of porous carbon material from na?ve biomass and highlights the great potential in wastewater treatment.

Efficient electrooxidation of biomass-derived aldehydes over ultrathin Ni V-layered double hydroxides films

Selective upgrading of C=O bonds to afford carboxylic acid is significant for the petrochemical industry and biomass utilization.Here we declared the efficient electrooxidation of biomass-derived aldehydes family over NiV-layered double hydroxides(LDHs) thin films.Mechanistic studies confirmed the hydroxyl active intermediate(-OH*) generated on the surface of NiV-LDHs films by employing electrochemical impedance spectroscopy and the electron paramagnetic resonance spectroscopy.By using advanced techniques,e.g.,extended X-ray absorption fine structure and high-angle annular dark-field scanning transmission electron microscopy,NiV-LDHs films with 2.6 nm could expose larger specific surface area.Taking benzaldehyde as a model,high current density of 200 mA cm^(-2)at 1.8 V vs.RHE,81.1% conversion,77.6% yield of benzoic acid and 90.8% Faradaic efficiency were reached,which was superior to most of previous studies.Theoretical DFT analysis was well matched with experimental findings and documented that NiV-LDHs had high adsorption capacity for the aldehydes to suppress the side reaction,and the aldehydes were oxidized by the electrophilic hydroxyl radicals formed on NiV-LDHs.Our findings offer a universal strategy for the robust upgrading of diverse biomass-derived platform chemicals.

In situ construction of Co/N/C-based heterojunction on biomass-derived hierarchical porous carbon with stable active sites using a Co-N protective strategy for high-efficiency ORR,OER and HER trifunctional electrocatalysts

The facile designs and fabrication of noble metal-free electrocatalysts are highly required to achieve multifunctional catalytic activity with excellent stability in Zn-air batteries,fuel cells and water splitting systems.Herein,a heterostructure engineering is applied to construct the high performance Co,Ncontaining carbon-based multifunctional electrocatalysts with the feature of isotype(i.e.n-n type Co_(2)N_(0.67)-BHPC)and anisotype(i.e.p-n type Co_(2)O_(3)-BHPC)heterojunctions for ORR,OER and HER.The nn type Co_(2)N_(0.67)-BHPC,in which biomass(e.g.mushroom)-derived hierarchical porous carbon(BHPC)incorporated with nonstoichiometric active species Co_(2)N_(0.67),is fabricated by using an in situ protective strategy of macrocyclic central Co-N_(4) from CoTPP(5,10,15,20-tetrakis(phenyl)porphyrinato cobalt)precursor through the intermolecularπ-πinteractions between CoTPP and its metal-free analogue H_(2) TPP.Meanwhile,an unprotected strategy of macrocyclic central Co-N_(4) from CoTPP can afford the anisotype Co_(2)O_(3)-BHPC p-n heterojunction.The as-prepared n-n type Co_(2)N_(0.67)-BHPC heterojunction exhibited a higher density of Co-based active sites with outstanding stability and more efficient charge transfer at the isotype heterojunction interface in comparison with p-n type Co_(2)O_(3)-BHPC heterojunction.Consequently,for ORR,Co_(2)N_(0.67)-BHPC exhibits the more positive onset and half-wave potentials of 0.93 and 0.86 V vs.RHE,respectively,superior to those of the commercial 20 wt%Pt/C and most of Cobased catalysts reported so far.To drive a current density of 10 mA cm^(-2),Co_(2)N_(0.67)-BHPC also shows the lower overpotentials of 0.34 and 0.21 V vs.RHE for OER and HER,respectively.Furthermore,the Zn-air battery equipped with Co_(2)N_(0.67)-BHPC displays higher maximum power density(109 mW cm^(-2))and charge-discharge cycle stability.Interestingly,the anisotype heterojunction Co_(2)O_(3)-BHPC as trifunctional electrocatalyst reveals evidently photoelectrochemical enhancement compared with the photostable Co_(2)N_(0.67)-BHPC.That is to say,isotype heterojunction material(n-n type Co^(2)N_(0.67)-BHPC)is equipped with better electrocatalytic performance than anisotype one(p-n type Co_(2)O_(3)-BHPC),but the opposite is true in photoelectrochemical catalysis.Meanwhile,the possible mechanism is proposed based on the energy band structures of the Co_(2)N_(0.67)-BHPC and Co_(2)O_(3)-BHPC and the cocatalyst effects.The present work provides much more possibilities to tune the electrocatalytic and photoelectrochemical properties of catalysts through a facile combination of heterostructure engineering protocol and macrocyclic central metal protective strategy.