Investigation of the influence for ZnSe phase in Ag2ZnSnSe4 and ZnO/Ag2ZnSnSe4 photoanodes on their photoelectrochemical activities in salt water solution

In this study, quaternary Ag₂ZnSnSe₄ (AZTSe) photoanodes with low and high ratios of ZnSe phase are made to understand the influence on the charge-transfer mechanisms, reaction kinetics and photoelectrochemical activities in electrolyte. Photoelectrochemical activities of 7.5 and 5.25 mA/cm² at the given voltage of 1 V (vs. Ag/AgCl) are obtained using the AZTSe sample containing low ratio (atomic percentage of around 21% in sample) and high ratio (atomic percentage of around 37% in sample) of ZnSe phase, respectively. From the electrochemical measurements and X-ray absorption spectra of samples, the ZnSe phase can attract the light-driven electrons from the sample with low ratio of ZnSe phase (atomic percentage of 21% in sample). However, for the sample containing high ratio of ZnSe phase (atomic percentage of 37% in sample), the ZnSe acts as the recombination center and results in poor photoelectrochemical activity. With the modification of ZnO rods on sample, its long-term photoelectrochemical activity is improved due to high charge transportation kinetic and photo-driven holes accumulation on ZnO rods rather than on AZTSe sample. Our study reports a significant observation on the influence of ZnSe phase for photoelectrochemical salt-water splitting.     

Construction of ZnO@NiO heterostructure photoelectrodes for improved photoelectrochemical performance

In this report, a p-n junction has been constructed using ZnO/NiO heterostructured photoelectrode by spin coating NiO layers over vertically aligned ZnO nanorod arrays to demonstrate its potential in water splitting applications. Before investigating their PEC performance, we thoroughly studied the introduction of NiO layers on the structure, morphology and light absorption property of ZnO nanorods. 9 layered NiO coated ZnO nanorods exhibited optimum photocurrent density of 0.251 mA/cm² at 0.8 V vs. Ag/AgCl which is attributed to its high absorbance and better charge transfer as recorded from UV–Vis and EIS data. Furthermore, we also studied the effect of (cation (Mg) and anion (Cl)) doping in PEC performance of ZnO nanorods on this optimized sample. Cl_ZnO/NiO showed high J_ph of 1.282 mA/cm² at 1.2 V vs. Ag/AgCl under visible light illumination. The reason behind better photoresponse is its enhanced absorption and well-defined p-n heterojunction between Cl_ZnO and NiO which favoured the separation and transfer of the photocarriers. The results displayed in this work provides a suitable approach of building p-n junction for high performance PEC water oxidation.     

CIS/CdS/ZnO/ZnO:Al modified photocathode for enhanced photoelectrochemical behavior under visible irradiation: Effects of pH and concentration of electrolyte solution

In this paper, the CuInS₂ films were firstly modified with CdS and CdS/ZnO/ZnO:Al/Au layers in order to improve the photoelectrochemical (PEC) water splitting efficiency. The CuInS₂ photoelectrode was synthesized by electrodeposition method as a facial and green method, on the FTO substrate. The effects of pH and concentration of Na₂S electrolyte solution on the photocurrent density of photoelectrode samples were studied. As a p-n junction photocathode, the CIS/CdS/ZnO/ZnO:Al/Au photoelectrode indicates the enhanced PEC activity. The photocurrent density of CIS/CdS/ZnO/ZnO:Al/Au photoelectrode reaches to 1.91 mA/cm², while is about 2.5 times higher than that for CuInS₂ film at pH = 8 (−0.6 V vs Ag/AgCl). The formation of a p-n junction at the CuInS₂ photoelectrode surface not only reduces the recombination of electron-hole pairs but also increases the PEC response and water splitting performance of the as-prepared CIS/CdS/ZnO/ZnO:Al/Au photoelectrode.     

Enhanced photoelectrochemical performance based on conformal and uniform ZnO/ZnSe/CdSe heterostructures on Zn foil substrate

The erosion issue of ZnO nanorod arrays (NRAs) film is the major obstacle in surface sensitization of ZnO NRAs grown on Zn foil substrate for photoelectrochemical (PEC) applications. In this paper, PEC performance of ZnO NRAs grown on Zn foil substrate was greatly enhanced by coating ZnSe and CdSe on the surface of ZnO NRAs. Dense ZnO NRAs were in-situ grown on seed-free Zn foil substrate in a NH₃·H₂O and NaOH hydrothermal system. ZnSe/CdSe co-sensitized ZnO heterostructures were then successfully synthesized using ZnO NRAs as precursors by two successive in-situ ion exchanges without damaging Zn foil and ZnO NRAs film. To obtain optimal photoconversion efficiency, anion exchange time and temperature were optimized. ZnO/ZnSe/CdSe heterostructures with optimized structure were shown as a layer of compact ZnSe/CdSe nanofilm conformally and uniformly coated on ZnO NRAs, which leads to efficient separation of photogenerated carriers, significant enhancement in visible-light absorption, and excellent PEC performance with photocurrent density of 3.008 mA/cm² (−0.2 V vs. Ag/AgCl) and photoconversion efficiency of 1.99% (0.418 V vs. RHE in polysulfide electrolyte solution), 27.55 and 40.61 times higher than those of ZnO NRAs, respectively.     

Copper oxide nanoparticle made by flame spray pyrolysis for photoelectrochemical water splitting - Part II. Photoelectrochemical study

A scalable method for hydrogen generation by splitting water via a photoelectrochemical cell was studied. Flame spray pyrolysis and spin coating processing methods were used for preparing copper oxide nanoparticles and copper oxide photocathodes. Copper oxide p-type semiconductor nanoparticles made by flame spray pyrolysis were spin coated on conducting ITO substrates and served as photocathodes for photoelectrochemical splitting of water. The film thickness was controlled by the concentration of the CuO suspension solution and numbers of layer deposited on the substrate. As sintering temperature increased to 600 °C, crystalline diameter increased from 28 nm (before sintering) to 110 nm and the bandgaps decreased from 1.68 eV to 1.44 eV. A 387 nm thickness CuO film with bandgap 1.44 eV was demonstrated to have 1.48% total conversion efficiency and 0.91% photon-to-hydrogen generation efficiency. The net photocurrent density (photocurrent - dark current) was measured to be 1.20 mA/cm² at applied voltage of −0.55 V vs. Ag/AgCl in 1 M KOH electrolyte with 1 sun (AM1.5G) illumination. Based on the Mott-Schottky plot, the carrier density was estimated to be 1.5 × 10²¹ cm⁻³ and the flatband potential to be 0.23 V vs. Ag/AgCl. Furthermore, the valence band edge and conduction band levels were found to lie at −5.00 eV and −3.56 eV respect to the vacuum respectively.     

Bifunctional electrocatalysts for water splitting from a bimetallic (V doped-NixFey) Metal–Organic framework MOF@Graphene oxide composite

An ongoing challenge still lies in the exploration of proficient electrocatalysts from earth-abundant non-precious metals instead of noble metal-based catalysts for clean hydrogen energy through large-Scale electrochemical water splitting. However, developing a non-precious transition metals based, stable electrocatalyst for cathodic hydrogen evolution reaction (HER) and anodic oxygen evolution reaction (OER) is important challenge for modern energy conversion technology. In this report Vanadium doped bimetallic nickel-iron nanoarray, fabricated by carbon supported architecture through carbonization process for electrochemical water splitting. Three types of catalysts were prepared in different molar ratio of Ni/Fe. The electrocatalytic performance demonstrated that the catalyst with equal mole ratio (0.06:0.06) of Ni/Fe possess high catalytic activity for both OER and HER in alkaline and acidic medium. Besides, our findings revealed that the doping of vanadium could play a strong synergetic effect with Ni/Fe, which provide a small overpotential of 90 mV and 210 mV at 10 mA cm^?2 for HER and OER respectively compared to the other two catalyst counterparts. Also, the catalyst with 1:1 (Ni/Fe) molar ratio showed a high current density of 208 mA cm^?2 for HER at 0.5 M H₂SO₄ and 579 mA cm^?2 for OER at 1 M KOH solution, the both current densities are much higher than the other two catalysts (different Ni/Fe ratio). In addition, the presented catalysts showed extremely good durability, reflecting in more than 20 h of consistent Chronoamprometry study at fixed overpotential η = 250 mV without any visible voltage elevation. Similarly, the (Ni/Fe) equal ratio catalyst showed better corrosion potential 0.209 V vs Ag/AgCl and lower current density 0.594 × 10^?12 A cm^?2 in high alkaline medium. The V-doping, MOF/GO surface defects are significantly increased the corrosion potential of the V-Ni_xFe_y-MOF/GO electrocatalyst. Besides, the water electrolyzed products were analysed by gas chromatography to get clear insights on the formed H₂ and O₂ products.     

Cu2S/Ni3S2 ultrathin nanosheets on Ni foam as a highly efficient electrocatalyst for oxygen evolution reaction

It is an inevitable choice to find efficient and economically-friendly electrocatalysts to reduce the high overpotential of oxygen evolution reaction (OER), which is the key to improve the energy conversion efficiency of water splitting. Herein, we synthesized Cu₂S/Ni₃S₂ catalysts on nickel foam (NF) with different molar ratios of Ni/Cu by a simple two-step hydrothermal method. Cu₂S/Ni₃S₂-0.5@NF (CS/NS-0.5@NF) effectively reduces the overpotential of OER, displaying small overpotentials (237 mV@100 mA cm^?2 and 280 mV@500 mA cm^?2) in an alkaline solution, along with a low Tafel slope of 44 mV dec^?1. CS/NS-0.5@NF also presents an excellent durability at a relatively high current density of 100 mA cm^?2 for 100 h. The excellent performance is benefited by the prominent structural advantages and desirable compositions. The nanosheet has a high electrochemical active surface area and the porous structure is conducive to electrolyte penetration and product release. This work provides an economically-friendly Cu-based sulfide catalyst for effective electrosynthesis of OER.     

Visible light driven photosplitting of water using one dimensional Mg doped ZnO nanorod arrays

In the present work, we have introduced Mg doped ZnO nanorods based photoanodes for photoelectrochemical water splitting applications. Vertically aligned Mg doped ZnO nanorods were fabricated by sol-gel and hydrothermal technique. The as-prepared nanorod samples exhibited hexagonal wurtzite structure as confirmed from XRD measurements. We achieved a photocurrent density of 0.35 mA/cm² at 1.5 V vs. Ag/AgCl for 10% Mg doped ZnO photoanode which is 9 times higher than that of undoped ZnO nanorods (0.03 mA/cm²). Incorporation of Mg resulted in faster charge transport and longer life time of electrons with reduced recombination rate. Mg dopant tuned the optical band gap of ZnO and increased the carrier concentration boosting the PEC performance of the photoanodes. Since seawater is one of the most abundant natural resource on earth, we further carried out seawater splitting of 10MgZ under visible light illumination which indicated its high photostability in natural seawater for 5 h of continuous illumination.     

Pt and Pt–Ag nanoparticles supported on carbon nanotubes (CNT) for oxygen reduction reaction in alkaline medium

In this work, we investigated the effect of the carbon nanotubes (CNT) as alternative support of cathodes for oxygen reduction reaction (ORR) in alkaline medium. The Pt and Pt–Ag nanomaterials supported on CNT were synthesized by sonochemical method. The crystalline structure, morphology, particle size, dispersion, specific surface area, and composition were investigated by XRD, SEM-EDS, TEM, HR-TEM, N₂ adsorption-desorption and XPS characterization. The electrochemical activity for ORR was evaluated by cyclic voltammetry (CV), linear sweep voltammetry (LSV), and electrochemical impedance spectroscopy (EIS) in alkaline medium. The electrochemical stability was researched by an accelerated degradation test (ADT). Pt/CNT showed the better electrocatalytic activity towards ORR compared with Pt–Ag/CNT and Pt/C. Pt/CNT exhibited higher specific activity (1.12 mA cm^?2 _Pt) than Pt/C (0.25 mA cm^?2 _Pt) which can be attributed to smaller particle size, Pt-CNT interaction, and Pt load (5 wt%). The Pt monometallic samples supported on CNT and Vulcan showed higher electrochemical stability after ADT than Pt–Ag bimetallic. The ORR activity of all materials synthesized proceeded through a four-electron pathway. Furthermore, the EIS results showed that Pt/CNT exhibited the lower resistance to the transfer electron compared with conventional Pt/C and Pt–Ag/CNT.     

Electron fixation of Sn2+/Cu+ bimetallic catalyst on flexible carbon fiber cloth for highly converting gaseous CO2 to formate at moderate potential

Designing highly active and selective electrocatalysts for converting CO₂ into value-added chemicals and fuels by electrochemical method is still a challenge. Herein, we have successfully fabricated a lotus-like morphology of Sn/Cu alloy on carbon fiber cloth via a facile electrodeposition method followed by air-dried treatment. Owing to the presence of Sn²⁺ and Cu⁺ on the surface of Sn/Cu alloy, this bimetallic Sn/Cu electrode exhibits the outstanding FE of formate with a maximum value of 95.81% at ?1.07 V versus RHE, and the total current density at ?0.97 V versus RHE keeping unchanged at 33.78 mA cm^?2 under the 20 h electrolysis even with the replacement of electrolyte. This work provides an effective strategy for highly boosting the selective production of formate from electrochemical CO₂ reduction by stabilizing the intermediate valence of bimetallic alloy.     

Zn doped ZIF67-derived porous carbon framework as efficient bifunctional electrocatalyst for water splitting

The electrochemical splitting of water is considered to be an efficient and potential technique for producing clean hydrogen and oxygen. Although, there are lots of significant developments in composite of superior hydrogen evolution reaction (HER) or oxygen evolution reaction (OER) catalyst applied in water splitting currently, designing non-precious and low-cost bifunctional electrocatalysts with high performance is still an attractive challenging issue. In this article, we report a novel bifunctional electrocatalyst with cobalt-based nanoparticles (NPs) embedded in Zn-doped hierarchical porous three-dimension N-doped carbonization structure via an annealing process of metal organic frameworks (MOFs) connected by N-doped carbon nanotube (denoted as Co–Zn/PNC). This composite structure possesses the characteristics of more active sites, numerous mesopores and high conductivity. The resulting electrocatalyst (Co–Zn/PNC) can be used as both anode and cathode to roust the overall water splitting, getting a current density of 10 mA cm⁻² at a cell voltage of 1.63 V in 1.0 M KOH electrolyte.     

A highly active composite electrocatalyst Ni–Fe–P–Nb2O5/NF for overall water splitting

This work demonstrates a facile Nb₂O₅-decorated electrocatalyst to prepare cost-effective Ni–Fe–P–Nb₂O₅/NF and compared HER & OER performance in alkaline media. The prepared electrocatalyst presented an outstanding electrocatalytic performance towards hydrogen evolution reaction, which required a quite low overpotential of 39.05 mV at the current density of ?10 mA cm^?2 in 1 M KOH electrolyte. Moreover, the Ni–Fe–P–Nb₂O₅/NF catalyst also has excellent oxygen evolution efficiency, which needs only 322 mV to reach the current density of 50 mA cm^?2. Furthermore, its electrocatalytic performance towards overall water splitting worked as both cathode and anode achieved a quite low potential of 1.56 V (10 mA cm^?2).     

CoSe2@NiSe2 nanoarray as better and efficient electrocatalyst for overall water splitting

Electrocatalytic water splitting is identified as one of the most promising solutions to energy crisis. The CoSe₂@NiSe₂ materials were first prepared and in situ grown on nickel foam by typical hydrothermal and selenification process at 120 °C. The results show that the CoSe₂@NiSe₂ material used as the 3D substrates electrode can maximize the synergy between the CoSe₂ and NiSe₂, and also exhibits high efficiency of water splitting reaction. The lower overpotential of only 235 mV is presented to attain 20 mA cm⁻² compared to the benchmark of RuO₂ electrodes (270 mV @ 20 mA cm⁻²). Besides, the CoSe₂@NiSe₂ material also shows a remarkable improved hydrogen evolution reaction activity compared to NiSe₂ (192 mV@10 mA cm⁻²) and Co precursor catalysts (208 mV@10 mA cm⁻²) individually, which a low overpotential of only 162 mV is achieved at 10 mA cm⁻². The CoSe₂@NiSe₂ catalysts exhibit excellent water splitting performance (cell voltage of 1.50 V@ 10 mA cm⁻²) under alkaline conditions. It was proved that the high water splitting performance of the catalyst is attributed to high electrochemical activity area and synergistic effect. The work offers new ideas for the exploitation of synergistic catalysis of composite catalysts and adds new examples for the exploitation of efficient, better and relatively non-toxic electrocatalysts.     

Rapid microwave synthesis of Cu2ZnSnS4 nanocrystals for photovoltaic junctions

Copper zinc tin sulfide ( CZTS) nanocrystal (NC) ink was prepared using thiourea as sulphur source by microwave assisted process. Thin films fabricated by doctor blading technique were then used to analyze the structure and morphology of the CZTS NCs. Variation in the properties of the NCs with varying Zn content in the precursor solution was studied. A Zn/Sn ratio of 1.4 with a Cu/(Sn + Zn) ratio of 0.8 in the starting solution was identified as an optimum compositional ratio to get good optoelectronic properties. Synthesis of CZTS NCs was done in ethylene glycol solvent and in a solvent which is a 1:1 mixture of isopropanol and poly ethylene glycol. The films developed from the latter ink showed better morphological and optoelectronic properties. CZTS thin films show absorption coefficient of the order of 10⁴ cm^?1 and optical band gap of 1.5 eV. The electrical resistivity was found to be 2.5 × 10² Ω/cm and hole mobility 0.051 cm²/ (Vs). Glass/FTO/CdS/CZTS multilayer structures were fabricated to form P‐N junctions. A knee voltage of 0.8 V from the I‐V characteristics of the PN junction indicates that a good V_oc can be expected from a solar cell constructed with CZTS ink as absorber layer.     

(Fe,Ni)S2@MoS2/NiS2 hollow heterostructure nanocubes for high-performance alkaline water electrolysis

Hollow hybrid heterostructures are regarded to be promising materials as bifunctional electrocatalysts for highly efficient water electrolysis due to their intriguing morphological features and remarkable electrochemical properties. Herein, with FeNi-PBA as both a precursor and morphological template, we demonstrate the rational construct of cost-effective (Fe,Ni)S₂@MoS₂/NiS₂ hollow hybrid heterostructures as bifunctional electrocatalysts for alkaline overall water splitting. Microstructural analysis shows that the hybrid is a kind of hierarchical heterostructure composed of MoS₂/NiS₂ nanosheets/nanoparticles in situ grown on hollow (Fe,Ni)S₂ nanocubes with abundant heterointerfaces, which effectively maximizes the electrochemical active sites to the accessible electrolyte ions, leading to the promoted charge transfer. As expected, the hybrid shows remarkable alkaline electrocatalytic performance, such as hydrogen evolution overpotential of 176 mV and oxygen evolution overpotential of 342 mV at 50 mA cm^?2, as well a cell voltage of 1.65 V at 20 mA cm^?2. Moreover, the stability and durability are greatly enhanced under harsh electrochemical conditions. This study opens a new venue for developing earth-abundant bifunctional electrocatalysts with hollow hybrid heterostructures for alkaline water electrolysis in the future.     

Overall noble metal free Ni and Fe doped Cu2ZnSnS4 (CZTS) bifunctional electrocatalytic systems for enhanced water splitting reactions

Herein, we report an inexpensive synthesis of sonochemical nickel and iron (M = Ni, Fe) doped Cu₂ZnSnS₄ (CZTS) and their utility as a nanoelectrodes for improved electrocatalytic water splitting performance. The as-synthesized electrode materials were characterized further by Transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman and X-ray photoelectron (XP) spectroscopic studies. Significantly, Ni doped CZTS electrocatalyst exhibits low overpotential approximately 214 and 400 mV for the hydrogen evolution reactions (HER) in 0.5 M H₂SO₄ and 1 M KOH electrolyte solutions respectively, and 1.29 V vs RHE for the oxygen evolution reactions (OER) in 1 M KOH at 10 mA/cm² current density. Small Tafel slopes and tested durability for longer time i.e. upto 500 min for water splitting, demonstrates that Ni doped CZTS is efficient bifunctional electrocatalyst having high activity along with extraordinary current/potential stability. Moreover, Fe doped CZTS electrocatalyst shows relatively poor response, i.e. overpotential 300 mV in 0.5 M H₂SO₄ and 445 mV in 1.0 M KOH towards HER and overpotential 1.54 V for the OER in 1 M KOH reaches at 10 mA/cm². This highly efficient bifunctional electrocatalysts that can meet the existing energy anxiety.     

Preparation and characterization of copper oxide particles/polypyrrole (Cu2O/PPy) via electrochemical method: Application in direct ethanol fuel cell

The electrocatalytic performance of Polypyrrole-Copper oxide particles modified carbon paste electrode (Cu₂O/PPy/CPE) for electrocatalytic oxidation of ethanol was reported for the first time in alkaline media. The composite Cu₂O/PPy was prepared using a facile approach consisting on the deposition of Polypyrrole film on CPE using galvanostatic mode then followed by the deposition of Copper particles at a constant potential. Scanning electron spectroscopy (SEM), infrared spectroscopy (FTIR), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were employed to characterize the structural and electrochemical properties of the Cu₂O/PPy/CPE and to explain the mechanism of electrooxidation of ethanol. The experimental parameters that influence the electrooxidation of ethanol were investigated and optimized. Our findings suggest that the electrodeposition of Copper particles on Polypyrrole film enhanced the catalytic activity towards the ethanol oxidation with a peak current density of 2.25 mA cm⁻² at 0.8 V vs Ag/AgCl, which is 2.6 times higher than the peak current density obtained by PPy/CPE electrode. It important to note that the saturation limit reaches a value of 5 M. To summarize, the good catalytic activity, stability and easy preparation make the Cu₂O/PPy composite as an excellent electrocatalyst for ethanol oxidation.     

MOF-derived multi-metal embedded N-doped carbon sheets rich in CNTs as efficient bifunctional oxygen electrocatalysts for rechargeable ZABs

The rational design and preparation of bifunctional electrocatalysts with pleasant oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) performance is crucial for extensive commercial applications of rechargeable Zn–air batteries (ZABs). Herein, we report a simple method to obtain multi-metal (Fe, Ni, Zn) embedded in N-doped carbon sheets entangled with carbon nanotubes (CNTs) as superior oxygen electrocatalysts (FeNi-NCS-2). The resultant FeNi-NCS-2 exhibits an impressive electrochemical performance, providing a reversible oxygen overpotential as low as 0.758 V. The ZAB with FeNi-NCS-2 as the air cathode shows a promising capacity of 639.71 mAh g^?1 at 20 mA cm^?2, a power density of 109.8 mW cm^?2 and cycling stability of over 130 cycles at 10 mA cm^?2 with an energy efficiency of about 55%, superior to the ZAB based on Pt/C–IrO₂. The satisfactory electrocatalytic performance is mainly due to the Fe, Ni-based nanoparticles protected by graphitic carbon layers, hierarchical porous lamellar structures that promote the accessibility between the active centers and the electrolyte as well as self-growing tangled carbon nanotubes that provide fast transmission channels. This study presents a facile way for the synthesis of highly efficient ORR/OER bifunctional electrocatalysts for high-performance rechargeable ZABs.     

The electropositive environment of Rh in Rh1Sn2/SWNTs for boosting trifunctional electrocatalysis

Designof the high-efficiency multifunctional electrocatalysts is highly demanded for many electrochemical energy devices, such as water electrolyzers, metal-air batteries and fuel cells. Here, Rh–Sn bimetallic nanocrystal catalysts supported on single-walled carbon nanotubes (Rh_xSn_y/SWNTs) are reported, and the Rh₁Sn₂/SWNTs electrocatalyst show best multifunctional electrocatalytic performance. Strong electron synergy between Rh and Sn is the source of high catalytic activity.Sn transfers electrons from Rh to Sn, forming a unique positive environment around Rh, which effectively optimizes the binding energy of the reaction intermediate and further improves the catalytic activity. An alkaline electrolyzer using Rh₁Sn₂/SWNTs catalyst demands an ultra-low cell voltage of 1.56 V at the current density of 10 mA cm⁻² for overall water splitting. In addition, Rh₁Sn₂/SWNTs demonstrates good oxygen reduction reaction (ORR) performance, making it an excellent catalyst for long-life Zn-air batteries. This work provides a facile strategy for the development of multifunctional electrocatalysts for the highly demanded electrochemical energy technologies.     

Biomass derivative-based fibrous perovskite electrocatalysts with a hierarchical porous structure for oxygen reduction in alkaline media

The CaMnO₃ perovskites have been proposed as promising electrocatalysts for the oxygen reduction reaction (ORR) as substitutes for the noble metal. However, their ORR catalytic activities still need to be further improved. Herein, fibrous CaMnO₃ catalysts with hierarchical mesoporous/macroporous structures for the ORR were prepared through a simple ion exchange process with biomass derivative calcium alginate as a precursor. Optimization of the synthesis conditions, in particular, the La doping content, is conducted. The as-prepared CaMnO₃ shows superior ORR performance in alkaline media with a limited diffusion density of 6.13 mA cm⁻². Furthermore, the ORR performance was further promoted by La-doping. The optimal La-doped CaMnO₃ sample exhibits the most positive onset potential of −0.01 V, the most positive half-wave potential of −0.28 V (VS. Ag/AgCl), and a greatly enhanced limited diffusion density of 6.76 mA cm⁻². The improvement of catalytic activity for ORR can be attributed to the porous structure, the rich surface chemisorbed oxygen and the redox couple Mn³⁺/Mn⁴⁺. The as-prepared perovskite fibers have potential as low cost and efficient ORR catalysts.