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2025 Volume 44 Issue 7
2025, 44(7): 100600
doi: 10.1016/j.cjsc.2025.100600
Abstract:
Reducing the Ir loading while preserving catalytic performance and mechanical robustness in anodic catalyst layers remains a critical challenge for the large-scale implementation of proton exchange membrane water electrolysis (PEMWE). Herein, we present a structural engineering strategy involving neodymium-doped Ir/IrO2 (Nd–Ir/IrO2) hollow nanospheres with precisely adjustable shell thickness and cavity dimensions. The optimized catalyst demonstrates excellent oxygen evolution reaction (OER) performance in acidic media, achieving a remarkably low overpotential of 259 mV at a benchmark current density of 10 mA cm−2 while exhibiting substantially enhanced durability compared to commercial IrO2 and Ir/IrO2 counterparts. Notably, the Nd–Ir/IrO2 catalyst delivers a mass activity of 541.6 A gIr−1 at 1.50 V vs. RHE, representing a 74.5-fold enhancement over conventional IrO2. Comprehensive electrochemical analysis and advanced characterization techniques reveal that the hierarchical hollow architecture simultaneously addresses multiple critical requirements: (i) abundant exposed active sites enabled by an enhanced electrochemical surface area, (ii) optimized mass transport pathways through engineered porosity, and (iii) preserved structural integrity via a continuous conductive framework, collectively enabling significant Ir loading reduction without compromising catalytic layer performance. Fundamental mechanistic investigations further disclose that Nd doping induces critical interfacial Nd–O–Ir configurations that stabilize lattice oxygen, together with intensified electron effect among mixed valent Ir that inhibits the overoxidation of Ir active sites during the OER process, synergistically ensuring enhanced catalytic durability. Our work establishes a dual-modulation paradigm integrating nanoscale architectural engineering with atomic-level heteroatom doping, providing a viable pathway toward high-performance PEMWE systems with drastically reduced noble metal requirements.
Reducing the Ir loading while preserving catalytic performance and mechanical robustness in anodic catalyst layers remains a critical challenge for the large-scale implementation of proton exchange membrane water electrolysis (PEMWE). Herein, we present a structural engineering strategy involving neodymium-doped Ir/IrO2 (Nd–Ir/IrO2) hollow nanospheres with precisely adjustable shell thickness and cavity dimensions. The optimized catalyst demonstrates excellent oxygen evolution reaction (OER) performance in acidic media, achieving a remarkably low overpotential of 259 mV at a benchmark current density of 10 mA cm−2 while exhibiting substantially enhanced durability compared to commercial IrO2 and Ir/IrO2 counterparts. Notably, the Nd–Ir/IrO2 catalyst delivers a mass activity of 541.6 A gIr−1 at 1.50 V vs. RHE, representing a 74.5-fold enhancement over conventional IrO2. Comprehensive electrochemical analysis and advanced characterization techniques reveal that the hierarchical hollow architecture simultaneously addresses multiple critical requirements: (i) abundant exposed active sites enabled by an enhanced electrochemical surface area, (ii) optimized mass transport pathways through engineered porosity, and (iii) preserved structural integrity via a continuous conductive framework, collectively enabling significant Ir loading reduction without compromising catalytic layer performance. Fundamental mechanistic investigations further disclose that Nd doping induces critical interfacial Nd–O–Ir configurations that stabilize lattice oxygen, together with intensified electron effect among mixed valent Ir that inhibits the overoxidation of Ir active sites during the OER process, synergistically ensuring enhanced catalytic durability. Our work establishes a dual-modulation paradigm integrating nanoscale architectural engineering with atomic-level heteroatom doping, providing a viable pathway toward high-performance PEMWE systems with drastically reduced noble metal requirements.
2025, 44(7): 100601
doi: 10.1016/j.cjsc.2025.100601
Abstract:
Functionally graded materials (FGMs) are innovative materials distinguished by gradual variations in composition and structure, offering exceptional properties for diverse applications. Poly(ionic liquid)s (PILs), merging the characteristics of polymers and ionic liquids, have emerged as viable options for the development of FGMs given their tunable skeleton, ionic conductivity, and compatibility with various functional materials. This review highlights the latest advancements in the design strategies of FGMs based on porous PILs, focusing on single and multi-gradient structures. Furthermore, we also highlight their emerging applications in molecular recognition, sensing, adsorption, separation, and catalysis. By exploring the interplay between porosity, ionic functionality, and gradient architecture, this review offers perspectives on the prospects of PIL-based FGMs for tackling global challenges in energy, environment, and healthcare.
Functionally graded materials (FGMs) are innovative materials distinguished by gradual variations in composition and structure, offering exceptional properties for diverse applications. Poly(ionic liquid)s (PILs), merging the characteristics of polymers and ionic liquids, have emerged as viable options for the development of FGMs given their tunable skeleton, ionic conductivity, and compatibility with various functional materials. This review highlights the latest advancements in the design strategies of FGMs based on porous PILs, focusing on single and multi-gradient structures. Furthermore, we also highlight their emerging applications in molecular recognition, sensing, adsorption, separation, and catalysis. By exploring the interplay between porosity, ionic functionality, and gradient architecture, this review offers perspectives on the prospects of PIL-based FGMs for tackling global challenges in energy, environment, and healthcare.
2025, 44(7): 100602
doi: 10.1016/j.cjsc.2025.100602
Abstract:
In mass spectrometry, fragments with a mass higher than the original molecular ion provide valuable insights into the molecular structure and can guide the assembly and disassembly processes for chemical synthesis. Here, we report such an example and following up by modifying the solvothermal reaction conditions (temperature and time) it is possible to isolate the high mass species in crystalline form. [Zn4L4Cl4] (Zn4L4, L = N-methylbenzimidazole-2-methanolate) has a boat-like Zn4O4 core but electrospray ionization mass spectrometry (ESI-MS) of the solution of its crystals shows higher mass peaks of Zn5L5, Zn5L6 and Zn6L6 species. Thus, both disassembly and reassembly are highly probable processes. Consequently, [Zn(HL)2Cl2] (Zn1, L = N-methylbenzimidazole-2-methanolate), [Zn4L6Cl2] (Zn4L6, L = N-methylbenzimidazole-2-methanolate) and [Zn6L6Cl4(CH3O)2] (Zn6L6, L = N-methylbenzimidazole-2-methanolate) were prepared. The results of multistage ESI-MS of their dissolved crystals led to a proposed mechanism of their formation in the gas phase as follows: [Zn3L4] through [ZnL] → [ZnL(HL)] → [Zn(HL)2] → [Zn2L] → [Zn2L2] → [Zn2L3]. The mechanism was derived in conjunction with Gibbs free energies calculated using DFT of the fragments observed in the ESI-MS of Zn4L4, Zn4L6 and Zn6L6. This work reveals the complex of chemical reactions, involving fragmentation and unexpected combination, under mass spectrometry condition which allows one to synthesize the observed transients, leading to mechanism of formation by correlation of solid-state/solution structural information.
In mass spectrometry, fragments with a mass higher than the original molecular ion provide valuable insights into the molecular structure and can guide the assembly and disassembly processes for chemical synthesis. Here, we report such an example and following up by modifying the solvothermal reaction conditions (temperature and time) it is possible to isolate the high mass species in crystalline form. [Zn4L4Cl4] (Zn4L4, L = N-methylbenzimidazole-2-methanolate) has a boat-like Zn4O4 core but electrospray ionization mass spectrometry (ESI-MS) of the solution of its crystals shows higher mass peaks of Zn5L5, Zn5L6 and Zn6L6 species. Thus, both disassembly and reassembly are highly probable processes. Consequently, [Zn(HL)2Cl2] (Zn1, L = N-methylbenzimidazole-2-methanolate), [Zn4L6Cl2] (Zn4L6, L = N-methylbenzimidazole-2-methanolate) and [Zn6L6Cl4(CH3O)2] (Zn6L6, L = N-methylbenzimidazole-2-methanolate) were prepared. The results of multistage ESI-MS of their dissolved crystals led to a proposed mechanism of their formation in the gas phase as follows: [Zn3L4] through [ZnL] → [ZnL(HL)] → [Zn(HL)2] → [Zn2L] → [Zn2L2] → [Zn2L3]. The mechanism was derived in conjunction with Gibbs free energies calculated using DFT of the fragments observed in the ESI-MS of Zn4L4, Zn4L6 and Zn6L6. This work reveals the complex of chemical reactions, involving fragmentation and unexpected combination, under mass spectrometry condition which allows one to synthesize the observed transients, leading to mechanism of formation by correlation of solid-state/solution structural information.
2025, 44(7): 100603
doi: 10.1016/j.cjsc.2025.100603
Abstract:
A novel tetra-europium(III)-containing antimonotungstate, Na8.2[H2N(CH3)2]9[Na10.8(tar)4(H2O)20(Eu2Sb2W21O72)2]·44.5H2O (EuSbW, H4tar = dl-tartaric acid), has been synthesized and characterized. The dimeric polyoxoanion of EuSbW consists of two Dawson-like {Eu2Sb2W21} units bridged by four dl-tartaric acid ligands. The adjacent carboxyl and hydroxy groups in each tartaric acid simultaneously chelate with W and Eu atoms from different {Eu2Sb2W21} units, thereby forming the dimeric structure. EuSbW represents an extremely rare polyoxometalate where four tartaric acid ligands function as connectors to bridge two {Eu2Sb2W21} units. Additionally, EuSbW exhibits excellent catalytic activity and reusability in the oxidation of thioethers and alcohols, achieving 100% conversion and > 99% selectivity for various thioethers, and 85–100% conversion with 90–99% selectivity for diverse alcohols under mild conditions.
A novel tetra-europium(III)-containing antimonotungstate, Na8.2[H2N(CH3)2]9[Na10.8(tar)4(H2O)20(Eu2Sb2W21O72)2]·44.5H2O (EuSbW, H4tar = dl-tartaric acid), has been synthesized and characterized. The dimeric polyoxoanion of EuSbW consists of two Dawson-like {Eu2Sb2W21} units bridged by four dl-tartaric acid ligands. The adjacent carboxyl and hydroxy groups in each tartaric acid simultaneously chelate with W and Eu atoms from different {Eu2Sb2W21} units, thereby forming the dimeric structure. EuSbW represents an extremely rare polyoxometalate where four tartaric acid ligands function as connectors to bridge two {Eu2Sb2W21} units. Additionally, EuSbW exhibits excellent catalytic activity and reusability in the oxidation of thioethers and alcohols, achieving 100% conversion and > 99% selectivity for various thioethers, and 85–100% conversion with 90–99% selectivity for diverse alcohols under mild conditions.
2025, 44(7): 100604
doi: 10.1016/j.cjsc.2025.100604
Abstract:
Stimuli-responsive two-dimensional (2D) covalent organic frameworks (COFs) with precise structures and permanent porosity have been employed as platforms for sensors. The slight change of backbones inside frameworks leads to different electronic states by external stimuli, such as solvent, pH, and water. Herein, we introduced an alkynyl-based building block (ETBA) with high planarity to synthesize two imine-based alkynyl-COFs (ETBA-TAPE-COF and ETBA-PYTA-COF) with high yield, good crystallinity, and chemical stability. Due to the presence of acetylene bonds, ETBA-TAPE-COF does not adopt the completely overlapping AA stacking mode. Slight interlayer displacement occurs along the parallel direction relative to the acetylene linkages, which facilitates lower configurational energy. Additionally, the introduction of pyrene group contributes to high π-electron mobility of ETBA-PYTA-COF. The interactions between electron-withdrawing group (ETBA) and electron-donating group (PYTA) during the processes of protonation and intramolecular charge transfer (ICT) endow ETBA-PYTA-COF with excellent acidochromic and solvatochromic properties, respectively. Based on this, a fluorescence sensor is successfully established, which can be used for rapid response to trace amounts of water in organic solvents. In contrast, ETBA-TAPE-COF does not exhibit these photophysical properties due to its higher HOMO–LUMO gap compared to ETBA-PYTA-COF. This work proposes a new strategy for designing and preparing COFs with unique photophysical properties without introducing additional functional groups.
Stimuli-responsive two-dimensional (2D) covalent organic frameworks (COFs) with precise structures and permanent porosity have been employed as platforms for sensors. The slight change of backbones inside frameworks leads to different electronic states by external stimuli, such as solvent, pH, and water. Herein, we introduced an alkynyl-based building block (ETBA) with high planarity to synthesize two imine-based alkynyl-COFs (ETBA-TAPE-COF and ETBA-PYTA-COF) with high yield, good crystallinity, and chemical stability. Due to the presence of acetylene bonds, ETBA-TAPE-COF does not adopt the completely overlapping AA stacking mode. Slight interlayer displacement occurs along the parallel direction relative to the acetylene linkages, which facilitates lower configurational energy. Additionally, the introduction of pyrene group contributes to high π-electron mobility of ETBA-PYTA-COF. The interactions between electron-withdrawing group (ETBA) and electron-donating group (PYTA) during the processes of protonation and intramolecular charge transfer (ICT) endow ETBA-PYTA-COF with excellent acidochromic and solvatochromic properties, respectively. Based on this, a fluorescence sensor is successfully established, which can be used for rapid response to trace amounts of water in organic solvents. In contrast, ETBA-TAPE-COF does not exhibit these photophysical properties due to its higher HOMO–LUMO gap compared to ETBA-PYTA-COF. This work proposes a new strategy for designing and preparing COFs with unique photophysical properties without introducing additional functional groups.
2025, 44(7): 100619
doi: 10.1016/j.cjsc.2025.100619
Abstract:
Photoelectrochemical water oxidation reaction (PEC-WOR) as a sustainable route to produce H2O2 is attractive but limited by low activity and poor product selectivity of photoanodes due to limited photogenerated charge efficiency and unfavorable thermodynamics. Herein, by crystal orientation engineering, the WO3 photoanode exposing (200) facets achieves both superior WOR activity (15.4 mA cm−2 at 1.76 VRHE) and high selectivity to H2O2 (∼70%). Comprehensive experimental and theoretical investigations discover that the high PEC-WOR activity of WO3-(200) is attributed to the rapid photogenerated charge separation/transfer both in bulk and at interfaces of WO3-(200) facet, which reduces the charge transfer resistance. This, coupling with the unique defective hydrogen bonding network at the WO3-(200)/electrolyte interface evidenced by operando PEC Fourier transform infrared spectroscopy, facilitating the outward-transfer of the WOR-produced H+, lowers the overall reaction barrier for the PEC-WOR. The superior selectivity of PEC-WOR to H2O2 is ascribed to the unique defective hydrogen bonding network alleviated adsorption of ∗OH over the WO3-(200) facet, which specially lowers the energy barrier of the 2-electron pathway, as compared to the 4-electron pathway. This work addresses the significant role of crystal orientation engineering on photoelectrocatalytic activity and selectivity, and sheds lights on the underlying PEC mechanism by understanding the water adsorption behaviors under illumination. The knowledge gained is expected to be extended to other photoeletrochemical reactions.
Photoelectrochemical water oxidation reaction (PEC-WOR) as a sustainable route to produce H2O2 is attractive but limited by low activity and poor product selectivity of photoanodes due to limited photogenerated charge efficiency and unfavorable thermodynamics. Herein, by crystal orientation engineering, the WO3 photoanode exposing (200) facets achieves both superior WOR activity (15.4 mA cm−2 at 1.76 VRHE) and high selectivity to H2O2 (∼70%). Comprehensive experimental and theoretical investigations discover that the high PEC-WOR activity of WO3-(200) is attributed to the rapid photogenerated charge separation/transfer both in bulk and at interfaces of WO3-(200) facet, which reduces the charge transfer resistance. This, coupling with the unique defective hydrogen bonding network at the WO3-(200)/electrolyte interface evidenced by operando PEC Fourier transform infrared spectroscopy, facilitating the outward-transfer of the WOR-produced H+, lowers the overall reaction barrier for the PEC-WOR. The superior selectivity of PEC-WOR to H2O2 is ascribed to the unique defective hydrogen bonding network alleviated adsorption of ∗OH over the WO3-(200) facet, which specially lowers the energy barrier of the 2-electron pathway, as compared to the 4-electron pathway. This work addresses the significant role of crystal orientation engineering on photoelectrocatalytic activity and selectivity, and sheds lights on the underlying PEC mechanism by understanding the water adsorption behaviors under illumination. The knowledge gained is expected to be extended to other photoeletrochemical reactions.
2025, 44(7): 100620
doi: 10.1016/j.cjsc.2025.100620
Abstract:
The modulation of charge transfer pathways within type-I heterojunctions through interfacial electric field (IEF) engineering is of critical importance in promoting photocatalytic hydrogen evolution, effectively facilitating the separation of photogenerated charge carriers. In this study, we performed in-situ growth of two-dimensional ZnIn2S4 nanosheets on MnCo2O4.5 nanorods to construct an ohmic-like type-I ZnIn2S4/MnCo2O4.5 heterojunction for efficient photocatalytic hydrogen evolution. This ohmic-like charge transfer mechanism effectively addresses the intrinsic limitations inherent to conventional type-I heterojunctions neglecting IEF effects, particularly through IEF-induced enhancement of charge separation efficiency. Consequently, the optimized ZnIn2S4/MnCo2O4.5 photocatalyst demonstrates an outstanding photocatalytic hydrogen evolution rate of 20.9 mmol g−1 h−1, 14.9 times that of the bare ZnIn2S4. Furthermore, the ohmic-like charge transport behavior has been rigorously validated by integrated advanced experimental characterizations, including in-situ X-ray photoelectron spectroscopy (XPS), Kelvin probe force microscopy (KPFM), and surface photovoltage (SPV) measurements, which collectively provide robust evidence for the proposed mechanism. This work offers valuable insights into the design of high-efficient ohmic-like type-I heterojunction catalysts for photocatalytic H2 evolution.
The modulation of charge transfer pathways within type-I heterojunctions through interfacial electric field (IEF) engineering is of critical importance in promoting photocatalytic hydrogen evolution, effectively facilitating the separation of photogenerated charge carriers. In this study, we performed in-situ growth of two-dimensional ZnIn2S4 nanosheets on MnCo2O4.5 nanorods to construct an ohmic-like type-I ZnIn2S4/MnCo2O4.5 heterojunction for efficient photocatalytic hydrogen evolution. This ohmic-like charge transfer mechanism effectively addresses the intrinsic limitations inherent to conventional type-I heterojunctions neglecting IEF effects, particularly through IEF-induced enhancement of charge separation efficiency. Consequently, the optimized ZnIn2S4/MnCo2O4.5 photocatalyst demonstrates an outstanding photocatalytic hydrogen evolution rate of 20.9 mmol g−1 h−1, 14.9 times that of the bare ZnIn2S4. Furthermore, the ohmic-like charge transport behavior has been rigorously validated by integrated advanced experimental characterizations, including in-situ X-ray photoelectron spectroscopy (XPS), Kelvin probe force microscopy (KPFM), and surface photovoltage (SPV) measurements, which collectively provide robust evidence for the proposed mechanism. This work offers valuable insights into the design of high-efficient ohmic-like type-I heterojunction catalysts for photocatalytic H2 evolution.
2025, 44(7): 100621
doi: 10.1016/j.cjsc.2025.100621
Abstract:
Oxygen evolution reaction (OER), a critical half-reaction in photocatalytic overall water splitting for producing hydrogen, is a key step toward sustainable energy conversion. Conventional photocatalysts often suffer from limited light absorption and rapid charge recombination, hindering their further applications. To address these challenges, we have designed and synthesized a novel series of self-sensitized metal-organic frameworks (MOFs), Fe2MCDDB (M = Ni, Mn, or Co). By incorporating photosensitive ligands, we have achieved efficient charge separation and promoted the transfer of photogenerated electrons to the active metal sites for water oxidation. Among the series, Fe2NiCDDB exhibits exceptional OER activity, achieving an oxygen evolution rate of 125.3 μmol g−1 h−1 under visible light irradiation. Experimental and theoretical results reveal that the optimized electronic structure and prolonged excited-state lifetime of Fe2NiCDDB contribute to its enhanced catalytic performance. This work provides a promising strategy for designing two-in-one MOF photocatalysts for water oxidation.
Oxygen evolution reaction (OER), a critical half-reaction in photocatalytic overall water splitting for producing hydrogen, is a key step toward sustainable energy conversion. Conventional photocatalysts often suffer from limited light absorption and rapid charge recombination, hindering their further applications. To address these challenges, we have designed and synthesized a novel series of self-sensitized metal-organic frameworks (MOFs), Fe2MCDDB (M = Ni, Mn, or Co). By incorporating photosensitive ligands, we have achieved efficient charge separation and promoted the transfer of photogenerated electrons to the active metal sites for water oxidation. Among the series, Fe2NiCDDB exhibits exceptional OER activity, achieving an oxygen evolution rate of 125.3 μmol g−1 h−1 under visible light irradiation. Experimental and theoretical results reveal that the optimized electronic structure and prolonged excited-state lifetime of Fe2NiCDDB contribute to its enhanced catalytic performance. This work provides a promising strategy for designing two-in-one MOF photocatalysts for water oxidation.
2025, 44(7): 100622
doi: 10.1016/j.cjsc.2025.100622
Abstract:
Flexible circuit switches have been widely used in electronic devices due to their outstanding flexibility and operability. In order to expand the types of flexible circuit switch materials, we develop a unique composite material, which integrates a photoresponsive flexible substrate derived from a photoreactive coordination polymer (CP) with an elastic conductive adhesive tape (CAT) in this work. The photoreactive CP {[Cd(2,6-bpvn)(3,5-DBB)2]·DMF}n (1) is prepared through solvothermal reaction of Cd(NO3)2·4H2O with 2,6-bis((E)-2-(pyridin-4-yl)vinyl)naphthalene (2,6-bpvn) and 3,5-dibromobenzoic acid (3,5-HDBB). Upon irradiation with UV light, crystals of 1 can undergo [2 + 2] photocycloaddition reaction and exhibit photomechanical movements. The crystalline powder of 1 can be uniformly distributed in polyvinyl alcohol (PVA) to generate the composite film 1-PVA. After pasting a piece of CAT on the surface of a 1-PVA film, a conductive two-layer film of 1-PVA/CAT can be fabricated. This film bends rapidly upon UV light exposure, connecting the circuit and causing the bulb to light up. When the light source is removed, it reverts to its initial state and the circuit is disconnected and the bulb is extinguished. This process can be cycled at least 100 times, achieving precise turn-on and turn-off performances of the photocontrollable circuit switch.
Flexible circuit switches have been widely used in electronic devices due to their outstanding flexibility and operability. In order to expand the types of flexible circuit switch materials, we develop a unique composite material, which integrates a photoresponsive flexible substrate derived from a photoreactive coordination polymer (CP) with an elastic conductive adhesive tape (CAT) in this work. The photoreactive CP {[Cd(2,6-bpvn)(3,5-DBB)2]·DMF}n (1) is prepared through solvothermal reaction of Cd(NO3)2·4H2O with 2,6-bis((E)-2-(pyridin-4-yl)vinyl)naphthalene (2,6-bpvn) and 3,5-dibromobenzoic acid (3,5-HDBB). Upon irradiation with UV light, crystals of 1 can undergo [2 + 2] photocycloaddition reaction and exhibit photomechanical movements. The crystalline powder of 1 can be uniformly distributed in polyvinyl alcohol (PVA) to generate the composite film 1-PVA. After pasting a piece of CAT on the surface of a 1-PVA film, a conductive two-layer film of 1-PVA/CAT can be fabricated. This film bends rapidly upon UV light exposure, connecting the circuit and causing the bulb to light up. When the light source is removed, it reverts to its initial state and the circuit is disconnected and the bulb is extinguished. This process can be cycled at least 100 times, achieving precise turn-on and turn-off performances of the photocontrollable circuit switch.
2025, 44(7): 100623
doi: 10.1016/j.cjsc.2025.100623
Abstract:
Photoelectrochemical (PEC) hydrogen production holds great promise for applications in energy production. A novel strategy characterized by simplicity, stability, and high efficiency is developed to significantly boost the PEC performance of TiO2 (anatase) nanotube arrays (TNTAs). This strategy entails a series of treatments, including a conventional anodic oxidation (etching) process, a primary annealing treatment, and a secondary annealing treatment via impregnation. As a result, nickel phosphide (Ni2P) is composited onto well-ordered titanium dioxide (anatase) nanotube array photoanodes (Ni2P/TNTAs), which exhibit hugely improved PEC H2 generation performance. A thorough and systematic investigation is conducted to comprehensively analyze the morphology, semiconductor band-gap structure, and PEC H2 production performance of the Ni2P/TNTAs composites. The experimental results demonstrate that under identical experimental circumstances, the measured photocurrent density of the Ni2P/TNTAs photoanode exhibits a 6.63-fold increase relative to that of TNTAs. The H2 production rate of Ni2P/TNTAs reaches 182.96 μmol/cm2, 6.10 times higher than that of pure TNTAs. The excellent interfacial charge transfer pathway at the Ni2P/TiO2 interface promotes photogenerated carrier separation and electron transfer from TiO2 to Ni2P. This method offers a valuable reference for designing highly efficient PEC H2-production catalysts.
Photoelectrochemical (PEC) hydrogen production holds great promise for applications in energy production. A novel strategy characterized by simplicity, stability, and high efficiency is developed to significantly boost the PEC performance of TiO2 (anatase) nanotube arrays (TNTAs). This strategy entails a series of treatments, including a conventional anodic oxidation (etching) process, a primary annealing treatment, and a secondary annealing treatment via impregnation. As a result, nickel phosphide (Ni2P) is composited onto well-ordered titanium dioxide (anatase) nanotube array photoanodes (Ni2P/TNTAs), which exhibit hugely improved PEC H2 generation performance. A thorough and systematic investigation is conducted to comprehensively analyze the morphology, semiconductor band-gap structure, and PEC H2 production performance of the Ni2P/TNTAs composites. The experimental results demonstrate that under identical experimental circumstances, the measured photocurrent density of the Ni2P/TNTAs photoanode exhibits a 6.63-fold increase relative to that of TNTAs. The H2 production rate of Ni2P/TNTAs reaches 182.96 μmol/cm2, 6.10 times higher than that of pure TNTAs. The excellent interfacial charge transfer pathway at the Ni2P/TiO2 interface promotes photogenerated carrier separation and electron transfer from TiO2 to Ni2P. This method offers a valuable reference for designing highly efficient PEC H2-production catalysts.
2025, 44(7): 100624
doi: 10.1016/j.cjsc.2025.100624
Abstract:
