Nitrogen-doped Hollow Carbon Research Articles

Anchoring cobalt dual-atom pairs on open hollow-structured carbon via a facile in-situ synthetic strategy for enhanced advanced oxidation processes

Atomically dispersed catalysts offer unprecedented opportunities for high-efficiency Fenton-like oxidation of organic pollutants in water. However, the hazardous metal leaching of atomically dispersed catalysts hinders their practical application for wastewater treatment, while the inaccessible interior active sites in carbon substrates have been commonly overlooked. Herein, we develop a straightforward approach for tightly anchoring cobalt dual-atom pairs on nitrogen-doped open hollow carbon structure (Co-NOHC) via an in-situ polyelectrolyte nanosphere-guided strategy. The unique open hollow carbon structure benefits the electron/mass transfer and maximizes the exposure of active sites. As a result, the as-synthesized Co-NOHC exhibits outstanding peroxymonosulfate activation activity and Fenton-like performance in oxidation by taking rhodamine B degradation as an example. Remarkably, the turnover frequency of the Co-NOHC is 6.5, 26.5, and 9.3 times higher than that of the Co2+, cobalt, and its oxides, respectively, and its catalytic activity also greatly outperforms the pristine zeolitic-imidazole frameworks derived Co-based atomically dispersed catalysts. More importantly, benefitted from the stable anchoring of cobalt dual atoms, the Co2+ leaching from the Co-NOHC is greatly alleviated, as low as 0.1 mg/L after the catalytic reaction, showing outstanding stability as compared to most atomically dispersed catalysts. Furthermore, the reactive active species, including SO4−, OH and O2− radicals, and electron-transfer mechanism are demonstrated to dominate the rhodamine B removal. This work offers a new consideration for promoting the development of the advanced catalysts and their potential applications in advanced oxidation process.

Electrochemical sensing for simultaneous determination of dopamine and acetaminophen based on ZIF-8@ZIF-67 derived Co/Mo2C embedded in N-doped carbon hollow nanocages

The exploration of an economical and efficient noble metal-free heterogeneous catalyst is of great significance for the construction of an electrochemical method for the simultaneous detection of Dopamine (DA) and acetaminophen (AC). In this paper, we employed a facile strategy to obtain Co/Mo2C nanoparticles embedded in nitrogen-doped carbon hollow nanocages (Co/Mo2C@N-C HNCs) heterogeneous structure by pyrolyzing ZIF-8@ZIF-67 precursor. The unique hollow structure ensures a fast electron transport channel, N doping regulates the local electronic structure of the catalyst, and the synergistic effect with Mo2C and Co nanoparticles provides more electrocatalytic active sites. The Co/Mo2C@N-C HNCs electrode separates the overlapping voltammetry peaks of DA and AC into two distinct voltammetry peaks (△E=200 mV), thereby selectively determining DA in the presence of AC and vice versa. The transfer coefficient (α) and electron transfer number (n) of DA and AC electrocatalytic oxidation were also studied. Using Co/Mo2C@N-C HNCs as electrode, an electrochemical sensor platform for the simultaneous detection of acetaminophen (AC) and dopamine (DA) was first constructed with linear range of 1–185 μM, and 1–100 μM and low detection limit of 0.35 μM and 0.46 μM for AC and DA, respectively. Satisfactory results have been obtained in the determination of human serum and acetaminophen tablets samples. DFT calculation reveals the molecular mechanisms for DA and AC interacting with the Co/Mo2C@N-C HNCs catalysts. This strategy provides a new idea for the selective determination of several analytes in complex substrates.

Secondary metal ion-induced electrochemical reduction of U(VI) to U(IV) solids

Recent studies have shown that aqueous U(VI) ions can be transformed into U(VI) precipitates through electrocatalytic redox reactions for uranium recovery. However, there have been no reports of U(IV) solids, such as UO2, using electrochemical methods under ambient conditions since low-valence states of uranium are typically oxidized to U(VI) by O2 or H2O2. Here we developed a secondary metal ion-induced strategy for electrocatalytic production of U(IV) solids from U(VI) solutions using a catalyst consisting of atomically dispersed gallium on hollow nitrogen-doped carbon capsules (Ga-Nx-C). This method relies on the presence of secondary metal ions, e.g., alkaline earth metals, transition metals, lanthanide metals, and actinide metals, which promote the generation of UO2 or bimetallic U(IV)-containing oxides through a two-electron transfer process. No U(IV) solid products were generated in the presence of alkali metal ions. Mechanistic studies revealed that the strong binding affinity between U(IV) and alkaline earth metals (Ca2+/Mg2+/Sr2+/Ba2+), transition metals (Ni2+/Zn2+/Pb2+/Fe3+, etc.) and lanthanide/actinide metals (Ce4+/Eu3+/Th4+/La3+) suppressed re-oxidation of U(IV) to U(VI), leading to the generation of U(IV)O2 and Mx(M = Ce, Eu, Th, La)U(IV)yO2. This work provides fundamental insights into the electrochemical behavior of uranium in aqueous media, whilst guiding uranyl capture from nuclear waste and contaminated water.

Hollow Ni/NiO@N-doped porous carbon for lithium ion battery anode based on dual-buffering strategy

As a promising anode material of lithium-ion batteries (LIBs), the poor electrical conductivity and severe volume expansion during cycling of nickel oxide (NiO) greatly limit its practical application. Here, a hollow nitrogen-doped porous carbon-loaded hollow Ni/NiO nanocomposite (Ni/NiO@HNC) was obtained by introducing Ni2+ into hollow covalent organic framework (HCOF) and then calcining the Ni2+/HCOF. The as-prepared Ni/NiO is nanoscale and hollow, which effectively accommodates the expanded volume of NiO. Hollow nitrogen-doped porous carbon (HNC) obtained from HCOF can further accommodate the expanded volume of NiO. The residual Ni and HNC can improve the electrical conductivity of Ni/NiO@HNC greatly. The regular pores of HNC inherited from HCOF facilitate the Li+ transfer. Thus, the Ni/NiO@HNC-2 composites exhibited outstanding cycle stability and rate performance when utilized as anode materials in LIBs. Even after 200 cycles at 0.1 A g−1, the capacity was still kept at 695.1 mAh g−1. The work provides an idea to prepare LIBs anodes based on dual-buffering strategy.

Curvature strain tunes electron transfer accelerates peroxymonosulfate activation to achieve high-efficiency advanced oxidation

The development of high performance and stable heterogeneous catalysts is conducive to promoting the advanced oxidation process (AOPs) to promote the degradation of organic pollutants efficiently, low-cost and environmentally friendly. Here nitrogen-doped hollow carbon spheres (NHCSs) and rigid organic molecule were used to create space confinement and complexation confinement conditions, respectively, and an advanced single-atom catalyst capable of strongly activating peroxymonosulfate (PMS) to degrade organic pollutants was finally constructed. The AOPs system driven by CoNC/NHCSs (20 mg) combined with PMS (20 mg) can degrade nearly 100 % of 20 mg/L (100 mL) bisphenol A (BPA, a microplastic) pollutant within 30 min, and the mineralization rate is up to 70.5 %. Face the complex water environment, such as sewage containing coexisting anions and cations, or acidic or alkaline sewage, the CoNC/NHCSs/PMS system still has high catalytic stability, and universality for other organic pollutants. The filter column with CoNC/NHCSs as the core also realizes the continuous purification of organic pollutants, which shortens the distance between laboratory research and practical application. Radical quenching and electron paramagnetic resonance techniques confirmed that CoNC/NHCSs activated PMS to SO4·−, ·OH, and 1O2, and these reactive oxygen species combined to eliminate organic pollutants. Density functional theory (DFT) calculations jointly confirm that the strong activation of PMS by CoNC/NHCSs is the key to achieving efficient degradation of organic pollutants, and the activity of CoNC/NHCSs is derived from high exposure rate of active sites and curvature effect caused by structural bending.

Balanced Polysulfide Containment and Lithium Ion Transport in Lithium-Sulfur Batteries via Nitrogen-doped Carbon Hollow Multi-shelled Structures on Modified Separators

Balanced Polysulfide Containment and Lithium Ion Transport in Lithium-Sulfur Batteries via Nitrogen-doped Carbon Hollow Multi-shelled Structures on Modified Separators

N-doped CNTs/CoNi nanochains-carbon hollow microspheres multi-level multi-scale heterogeneous interface structures and microwave absorption properties

Constructing multi-level multi-scale heterogeneous interfaces in magnetic carbon-based composites remains a formidable challenge, requiring rational material combinations to effectively balance dielectric and magnetic losses for achieving high strength and wide frequency wave absorption. Electromagnetic wave (EMW) absorbing materials consisted of cobalt-nickel (CoNi) magnetic nanochain, nitrogen-doped carbon nanotubes (NCNTs) and hollow carbon microspheres were prepared by hydrothermal method without external magnetic field. These composites possessed a unique multi-level multi-scale heterogeneous interface structure that is highly advantageous for efficient absorption of EMWs. The CoNi nanoparticles were self-assembled into uniformly distributed and randomly oriented magnetic nanochains, which were further reassembled with NCNTs and hollow carbon microspheres to form heterogeneous interface structures resembling a rose, chrysanthemum, hedgehog ball, and bauhinia tree. Due to the high-density interface enhancing the loss ability of interface polarization, as well as the higher saturation magnetization, coercivity, and wave absorption ability of the magnetic nanochains compared to the magnetic nanoparticles themselves, the minimum reflection loss achieved is −66.86 dB, and the effective absorption bandwidth achieved is 5.01 GHz, at a content as low as 11 wt%. This study provides a new idea for generating nanochains without magnetic fields and constructing multi-level and multi-scale heterogeneous interface structures to achieve strong absorption and wide effective absorption bandwidth (EAB).

Surface crystallized supramolecular to achieve highly dispersed ultrafine nano-palladium in-situ deposition to promote thermal/electrocatalytic reduction

To promote the greening and economization of industrial production, the development of advanced catalyst manufacturing technology with high activity and low cost is an indispensable part. In this study, nitrogen-doped hollow carbon spheres (NHCSs) were used as anchors to construct a supramolecular coating formed by the self-assembly of boron clusters and β-cyclodextrin by surface crystallization strategy, with the help of the weak reducing agent characteristics of boron clusters, highly dispersed ultra-small nano-palladium particles were in-situ embedded on the surface of NHCSs. The deoxygenation hydrogenation of nitroaromatics and the reduction of nitrate to ammonia were used as the representatives of thermal catalytic reduction and electrocatalytic reduction respectively. The excellent properties of the constructed Pd/NHCSs were proved by the probe reaction. In the catalytic hydrogenation of nitroaromatics to aminoaromatics, the reaction kinetic rate and activation energy are at the leading level. At the same time, the constructed Pd/NHCSs can also electrocatalytically reduce nitrate to high value-added ammonia with high activity and selectivity, and the behavior of Pd/NHCSs high selectivity driving nitrate conversion was revealed by density functional theory and in situ attenuated total reflection Fourier transform infrared (ATRFTIR) technique. These results all reflect the feasibility and superiority of in-situ anchoring ultra-small nano-metals as catalysts by surface crystallization to build a supramolecular cladding with reducing properties, which is an effective way to construct high-activity and low-cost advanced catalysts.

Nitrogen-doped hollow carbon sphere composite Mn3O4 as an advanced host for lithium-sulfur battery

As the most promising advanced energy storage system, lithium-sulfur batteries (LSBs) are highly favored by the researchers because of their advantages of high energy density (2500 W h kg−1), low cost and non-pollution. However, the low conductivity, volume expansion of sulfur, and shuttle effect are still the great hindrance to the practical application of LSBs. Herein, the above problems can be addressed through the following strategies: (1) Hollow carbon microspheres with high specific surface area were constructed as sulfur hosts to increase sulfur loading while also being able to enhance the physical adsorption of polysulfides; (2) the loading of Mn3O4 particles on the basis of hollow carbon microspheres facilitates the capture and adsorption of polysulfides; (3) the hollow carbon sphere structure as a conductive network can provide more pathways for rapid electrical/ionic transport and also accelerate electrolyte wetting. Moreover, the thinner shell of hollow carbon microsphere is conducive to ion diffusion and speed up the reaction rate. Thus, the NHCS/Mn3O4/S composites exhibit a high discharge specific capacity of 1010.3 mAh g−1 at first and still maintained a reversible capacity of 269.2 mAh g−1 after 500 cycles. This work presents a facile sustainable and efficient synergistic strategy for the development of advanced LSBs.

Repairable body-centered cubic Fe0 anchoring on porous hollow nitrogen-doped carbon spheres with adjusting electron distribution for efficient electrocatalytic ammonia synthesis

Electrocatalytic nitrogen reduction reaction (ENRR) is a promising and efficient method for ammonia production. However, ENRR is restricted by the adsorption and activation of N2. Herein, an efficient nitrogen reduction reaction (NRR) electrocatalyst loaded with zero valent iron (ZVI) particles onto porous nitrogen-doped carbon (NC) hollow spheres is reported. The optimal Fe@10N3C-950 exhibits excellent performance with high ammonia (NH3) yield (152.28 µg h−1 mgcat−1) and Faradaic efficiency (FE, 54.55 %) at − 0.3 V (versus reversible hydrogen electrode, vs. RHE). Bader charge shows that the adsorbed N2 acquires more electrons from Fe sites with body-centered cubic (BCC) structure to better activate N2. Moreover, i-t experiments are performed before electrocatalytic NH3 production to effectively eliminate the effect of oxidation on ZVI and thus, maintain high ENRR activity for Fe@10N3C-950. Theoretical calculations indicate that nitrogen doping not only reduces the Gibbs free energy of rate determining step (RDS), but the BCC-structured Fe can also decrease the energy barriers of N2 activation and RDS.

Hemp-ball-like structured Fe3O4-hollow carbon sphere nanozymes functionalized carbon fiber cathode for efficient flow-through electro-Fenton

Electro-Fenton (EF) technology has been recognized as a highly promising electrochemical advanced oxidation process. Promoting effective contact between active species and contaminant is crucial in electrocatalysis. Herein, we had innovatively designed a unique nanozymes in the form of hemp-ball-like structures, consist of the uniform growth of Fe3O4 nanoparticles on nitrogen-doped nano hollow carbon spheres (NHCS). This catalyst was employed in a flow-through EF system with carbon felt (CF) filters serving as the work electrode. The active sites were fully exposed through the ultradispersed Fe3O4 nanoparticles, and the NHCS facilitated efficient cycling of Fe3+/Fe2+. The results showed that the generation capacity of hydroxyl radicals (·OH) was enhanced, and the oxidation flux reached 370.080 mg h−1m−2 with low energy consumption. The superiority of the hollow carrier was proved by the degradation results and COMSOL calculation for various carbon carriers. Moreover, the active catalyst exhibited adaptability in complex water matrices. This study offers a new perspective to synergize nanomaterials, EF reactions and flow-type systems.

ZIF67-derived ultrafine Co9S8 nanoparticles embedded in nitrogen-doped hollow carbon nanocages for enhanced performances of trifunctional ORR/OER/HER and overall water splitting

ZIF67-derived ultrafine Co9S8 nanoparticles embedded in nitrogen-doped hollow carbon nanocages for enhanced performances of trifunctional ORR/OER/HER and overall water splitting

Hierarchical porous cobalt nanoparticles encapsulated in heteroatom-doped hollow carbon as an enhancing multifunctional catalyst for hydrolysis of sodium borohydride and hydrogenation of bromate in water

Multifunctional heterogeneous catalysts have been consistently explored in recent years because of their distinctive catalytic activity in different catalysis areas at once. Here, a cobalt (Co) nanoparticles encapsulated in nitrogen-doped hollow carbon (denoted as Co@NHC) is prepared by two-step modifications of acid etching and high temperature carbonization in the inert atmosphere using a peculiar polyhedral configuration Co-ZIF as an initial template. Benefiting from an intriguing polyhedral configuration hollow structure with high specific surface area and pore volume supplying plentiful active sites, Co@NHC shows exceptional catalytic activity in catalyzing hydrolysis of NaBH4 and hydrogenation of toxic bromate in water. From experimental results, Co@NHC could efficiently enhance the generation of H2 with a H2 generation rate of 1515.4 mL min−1 gcat−1 meanwhile the activation energy (Ea) calculated from Co@NHC/NaBH4 system was only 12.6 kJ mol−1. Besides, the combination of Co@NHC and NaBH4 could further reduce toxic bromate ions into bromide via catalytic hydrogenation with a maximum bromate removal capacity of 390.6 μmol g−1. More importantly, due to its strong magnetization, Co@NHC could be simply recovered after reactions, making it well-preserve the unique structure as well as catalytic activity for multiple continuous recycles in both catalytic applications. Additionally, the plausible reaction mechanisms in catalyzing hydrolysis of NaBH4 and hydrogenation of bromate were also proposed. This work has pioneered a promising approach on preparing an engrossing magnetic heterogeneous Co-based catalyst that is practically applicable in various areas of catalysis.

Nanosheets-assembled hollow N-doped carbon nanospheres encapsulated with ultrasmall NiSe nanoparticles for electrocatalytic hydrogen evolution

Developing highly active and stably non-precious metal electrocatalysts for hydrogen production in alkaline conditions is of paramount importance to hydrogen economy. Herein, nanosheet-assembled hollow nitrogen-doped carbon nanospheres confined with ultrasmall NiSe nanoparticles (NiSe@NC) are synthesized by employing a SiO2 template-assisted approach. As expected, the as-prepared NiSe@NC electrocatalyst delivers an overpotential of 169 mV at the current density of 10 mA/cm2 without iR-correction, and sustains at least 80 h for continuous operation, far outperforming the NiSe-p catalyst in 1 M KOH medium toward hydrogen evolution reaction (HER). The appealing HER performance is mainly ascribed to the synergy effect between hollow nitrogen-doped carbon and highly active NiSe nanoparticles, which improves catalytically active sites, expedites electron transfer rate and optimizes the electronic structure of NiSe@NC nanomaterial. More strikingly, this study presents the feasible insights for constructing robust cost-effective electrocatalysts towards efficient HER in harsh alkaline media.

Hollow Nitrogen-Doped Carbon Spheres as Zincophilic Sites for Zn Flow Battery.

Severe dendrite growth on Zn anodes poses a significant challenge to the development of Zn-based batteries. An effective strategy for inhibiting the formation of Zn dendrites involves electrode modification. In this study, hollow nitrogen-doped carbon spheres (HNCS) are synthesized and used as electrodes to regulate Zn deposition in Zn-based flow batteries. The electrochemical performance of HNCS reveals that the pyrrole nitrogen of HNCS changes the electrode surface state. Therefore, HNCS can inhibit the hydrogen evolution reaction and achieve uniform Zn deposition. HNCS can effectively inhibit dendrite growth and improve the reversibility of the Zn plating/stripping process to regulate the reversibility of Zn-based batteries. The zinc-bromine redox flow battery assembled with HNCS significantly reduces the hydrogen evolution reaction and exhibits a coulombic efficiency of 90 % and energy efficiency of 73 % at a current density of 60 mA cm-2. Similarly, an alkaline zinc-iron flow battery can maintain high Coulombic efficiency and energy efficiency of 83 %.

A nitrogen-doped hollow carbon nanospheres-based aptasensor for non-invasive salivary detection of progesterone

Developing an easy-to-use and non-invasive sensor for monitoring progesterone (P4) as a multi-functional hormone is highly demanded for point-of-care testing. In this study, an ultrasensitive electrochemical aptasensor is fabricated for monitoring P4 in human biofluids. The sensing interface was designed based on the porous nitrogen-doped hollow carbon spheres (N-HCSs). The N-HCSs covalently immobilized high-dense aptamer (Apt) sequences as the bioreceptor of P4. The electron transfer of the redox probe was hindered by incubating P4 on the aptasensor surface and forming the P4-Apt complexes. Meanwhile, the signaling was decreased under two wide linear dynamic ranges (LDRs) from 10 fM to 5.6 μM with a limit of detection (LOD) value of 3.33 fM. The aptasensor presented satisfactory selectivity in the presence of different off-target species with successful feasibility for P4 detection in some human urine and saliva samples. The aptasensor with high sensitivity, as an advantage for on-site and sensitive measurement of P4, can be considered a non-invasive tool for routine analysis of real-world clinical samples method.

Short-Chain Sulfur Confined into Nitrogen-Doped Hollow Carbon Nanospheres for High-Capacity Potassium Storage.

Carbon-based materials are one of the ideal negative electrode materials for potassium ion batteries. However, the limited active sites and sluggish diffusion ion kinetics still hinder its commercialization process. To address these problems, we design a novel carbon composite anode, by confining highly reactive short-chain sulfur molecules into nitrogen-doped hollow carbon nanospheres (termed SHC-450). The formation process involves the controlled synthesis of hollow polyaniline (PANI) nanospheres as precursors via an Ostwald ripening mechanism and subsequent sulfuration treatment. The high content of constrained short-chain sulfur molecules (20.94 wt%) and considerable N (7.15 wt%) ensure sufficient active sites for K+ storage in SHC-450. Accordingly, the SHC-450 electrode exhibits a high reversible capacity of 472.05 mAh g-1 at 0.1 A g-1 and good rate capability (172 mAh g-1 at 2 A g-1). Thermogravimetric analysis shows that SHC-450 has impressive thermal stability to withstand a high temperature of up to 640 °C. Ex situ spectroscopic characterizations reveal that the short-chain sulfur provides high capacity through reversible formation of K2S. Moreover, its special hollow structure not only provides ample space for highly active short-chain sulfur reactants but also effectively mitigates volume expansion during the sulfur conversion process. This work offers new perspectives on enhanced K+ storage performance from an interesting anode design and the space-limited domain principle.

Optimizing Electron Spin-Polarized States of MoSe2/Cr2Se3 Heterojunction-Embedded Carbon Nanospheres for Superior Sodium/Potassium-Ion Battery Performances.

The principal challenges faced by sodium-ion batteries (SIBs) and potassium-ion batteries (KIBs) revolve around identifying suitable host materials capable of accommodating metal ions with larger dimensions and addressing the issue of sluggish chemical kinetics. Herein, a MoSe2/Cr2Se3 heterojunction uniformly embedded is fabricated in nitrogen-doped hollow carbon nanospheres (MoSe2/Cr2Se3@N-HCSs) as an electrode material for SIBs and KIBs. Cr2Se3 exhibits spontaneous antiparallel alignment of magnetic moments. Mo2+ doping is employed to regulate the electron spin states of Cr2Se3. Moreover, the MoSe2 and Cr2Se3 heterojunctions induce a lattice mismatch at the heterostructure interface, resulting in spin-polarized states or localized magnetic moments at the interface, potentially contributing to spin-polarized surface capacitance. MoSe2/Cr2Se3@N-HCSs demonstrate a high capacity of 498 mAh g-1 at 0.1 A g-1 with good cycling stability (capacity of 405 mAh g-1 and a coulombic efficiency of 99.8% after 1000 cycles). Additionally, density functional theory (DFT) calculations simulate the accumulation of spin-polarized charges at the MoSe2/Cr2Se3@N-HCSs heterojunction interface, dependent on the surface electron density of the antiferromagnetic Cr2Se3 and the surface spin polarization near the Fermi level. After regulating the electron spin states through Mo-doping, the band gap of the material decreases. These significant findings provide novel insights into the design and synthesis of electrode materials with exceptional performance characteristics for batteries.

Hydrodeoxygenation of furfural to 2-methylfuran over Cu-Co confined by hollow carbon cage catalyst enhanced by optimized charge transfer and alloy structure

Hydrodeoxygenation of furfural over non-noble metal catalyst is an effective route to synthesis 2-methylfuran, but the reaction is often hampered by the low activity and selectivity of the catalyst. Herein, a bimetallic catalyst with CuCo alloy encapsulated in a hollow nitrogen-doped carbon cages (CuCo/NC) are fabricated by using ZIF-67 as a sacrificial template, which exhibited superior catalytic performance and a full conversion of furfural with a 95.7 % selectivity towards 2-methylfuran was achieved at an under relatively mild reaction conditions (150 ℃, 1.5 MPa H2 and 4.0 h). The characterizations and density functional theory calculations clearly evidenced that the introduced Cu species acts as a switch to regulate the activity and selectivity of the catalyst via two aspects. On the one hand, the Cu species perturb the Co electronic structure leading to adsorption configuration of furfural change from flat to vertical on the catalyst surface, which successfully hindered the hydrogenation of furan ring, resulting high selectivity towards 2-methylfuran. On the other hand, the formed CuCo (111) sites promotes the dissociation of hydrogen, cleavage of the CO bond and reduces the diffusion barrier of hydrogen so as to advance the formation of 2-methylfuran. This work may provide a feasible strategy for the design of nanoalloy catalyst for the hydrodeoxygenation of biomass platforms to value-added chemicals.

Photoelectrothermocatalytic reduction of CO2 to glycol via CdIn2S4-N/C hollow heterostructure mimicking plant cell

A series of novel semiconductor composites of CdIn2S4-N/C, in which CdIn2S4 is grown on hollow nitrogen-doped carbon spheres to mimic plant cells, were designed and applied to photoelectrothermocatalytic reduction of CO2. Our results reveal that the unique hollow structure and photothermal properties of N/C contribute to excellent performance of catalyst in CO2 reduction. Specifically, the optimal catalyst of CdIn2S4-N/C-2–800 demonstrates an outstanding catalytic activity with a formation rate of 168.5 µM h−1 cm−2 for carbon-based products and an electron selectivity for C2 products of 66.9 %. DFT calculations demonstrate that pyridine N and pyrrole N can reduce the energy barrier during CO2 reduction. Two important species of *=C=O and OC-COH* were detected by operando IR spectra and suggested to be key intermediates to C2 products via a carbene (*=C=O) coupling mechanism. CdIn2S4-N/C provides thermoelectrons and active sites like in the membrane of plant to enhance the probability of C-C coupling.