Efficient Hydrogen Production Research Articles

Optimization of user-side electrolytic hydrogen production system considering electrolyzer efficiency degradation

This paper proposes an optimized operational strategy for user-side proton exchange membrane (PEM) electrolyzer hydrogen production systems, considering the degradation of hydrogen production efficiency over time. The work is divided into three parts. First, a combined hydrogen production efficiency model based on operational data is established, using polynomial surface fitting (PSF) and gaussian process regression (GPR) to model the electrolyzer's efficiency from two perspectives: operational time and input power. Second, an optimization model for the operational strategy of the user-side electrolytic hydrogen production system is constructed, aiming to enhance overall system efficiency by adjusting the electrolyzer's input power. Finally, the hydrogen efficiency model from the first part is applied to the optimization strategy in the second part for empirical analysis. The results show that the optimized strategy, which accounts for the degradation of hydrogen production efficiency, significantly improves system performance, validating the method's effectiveness and practicality. This study provides theoretical support and practical guidance for the efficient operation of user-side electrolyzers, contributing to the promotion and application of green hydrogen technologies.

Electrooxidation of glycerol to formic acid coupled with Energy-Saving hydrogen production over ruthenium doped Cobalt-Based nanosheet arrays

The utilization of small molecule oxidation reactions as a substitute for the sluggish oxygen evolution reaction (OER) in traditional water electrolysis represents an innovative approach to achieve efficient hydrogen production while concurrently generating value-added chemicals. Herein, we report an energy-saving H2 production system utilizing electrooxidation of glycerol to generate valuable formate. Cobalt–ruthenium oxide nanosheet arrays (CoRuO/CF) and cobalt–ruthenium bimetallic nanoparticles wrapped by nitrogen-doped carbon nanosheet arrays (CoRuCN/CF) were synthesized for glycerol oxidation reaction (GOR) and hydrogen evolution reaction (HER), respectively, using Co-ZIF nanosheets precursor material supported on copper foam (Co-ZIF/CF) as the substrate. Remarkably, the hybrid electrolysis system can achieve a current density of 10 mA cm−2 with only 1.19 V, which is significantly lower than that required by traditional water-splitting systems. This work demonstrates the promising potential of efficiently utilizing biomass energy and achieving a sustainable production process for fine chemical products.

Controlling size and distribution of Au nano-particles on C3N4 for high-efficiency photocatalytic hydrogen production.

With advantages such as low cost, high stability, and ease of production, visible light photocatalytic C3N4 with a unique microscopic layered structure holds significant potential for development. However, its hydrogen production efficiency remains low due to the pronounced recombination of photo-generated charge carriers and limited surface reaction sites. Normally, the photocatalytic performance of C3N4 can be enhanced by loading noble metals with surface plasmon resonance. It is worth noting that the size of noble metal nanoparticles has a great influence on photocatalytic performance. In this study, accurate controlling of the size and distribution of Au nanoparticles was achieved on the surface of C3N4 by introducing amino groups to improve photocatalytic performance. Results show that uniformly distributed Au nanoparticles in the range of 2-6nm can be obtained on C3N4 with a remarkable enhancement of hydrogen production efficiency, which is about 114 times the property of pure C3N4. The small-sized and uniformly distributed Au nanoparticles can provide more reaction sites and increase the separation of photo-generated charge carriers, in turn improving Au/NH3-C3N4 photocatalytic hydrogen release rate to 6.85 mmol g-1h-1. This work offers a facile way to enhance photocatalytic performance by controlling the size of metal nanoparticles on C3N4 precisely.

Tuning Electronic and Proton Transfer Properties on Amino-Functionalized Co-Based MOF for Efficient Photocatalytic Hydrogen Evolution.

Efficient hydrogen (H2) production through photocatalytic water splitting was achieved by using an amino-functionalized azolate/cobalt-based metal-organic framework (MOF). While previous reports highlighted the amino group's role only as a substituent group for enabling light absorption of MOFs in the visible region, our present study revealed its dual role. The amino substituent not only acts as an electron donor to increase the electron availability at the active Co sites but also provides hydrogen-hopping sites within the pore channel, facilitating proton (H+) diffusion along the framework. This dual functionality significantly boosts the performance of this Co-MOF as a hydrogen evolution cocatalyst. When combined with fluorescein and triethylamine as the photosensitizer and sacrificial agent, respectively, the Co-MOF achieved a remarkable H2 production rate of 27 mmol g-1 over 4 h. Notably, this performance surpasses those of benchmark platinum (Pt) and titanium dioxide (TiO2) cocatalysts.

Modulating Silver Performance in Electrocatalytic Oxidation of HCHO via SMSI between Ag-Co3O4 Interfaces.

The replacement of oxygen evolution reactions with organic molecule oxidation reactions to enable energy-efficient hydrogen production has been a subject of interest. However, further reducing reaction energy consumption and releasing hydrogen from organic molecules continue to pose significant challenges. Herein, a strategy is proposed to produce hydrogen and formic acid from formaldehyde using Ag/Co3O4 interface catalysts at the anode. The key to improving the performance of Ag-based catalysts for formaldehyde oxidation lies in the strong SMSI achieved through the well-designed "spontaneous redox reaction" between Ag and Co3O4 precursors. Nano-sized Ag particles are uniformly dispersed on Co3O4 nanosheets, and electron-deficient Agδ+ are formed by the SMSI between Ag and Co3O4. Ag/Co3O4 demonstrates exceptional formaldehyde oxidation activity at low potentials of 0.32V versus RHE and 0.65V versus RHE, achieving current densities of 10 and 100mA cm-2, respectively. The electrolyzer "Ag/Co3O4||20% Pt/C" achieves over 195% hydrogen efficiency and over 98% formic acid selectivity, maintaining stable operation for 60 hours. This work not only presents a novel approach to precisely modulate Ag particle size and interface electronic structure via SMSI, but also provides a promising approach to efficient and energy-saving hydrogen production and the transformation of harmful formaldehyde.

Numerical analysis of catalytic reaction kinetics in methanol steam reformer with variable cross-sectional channel

ABSTRACT Methanol steam reforming (MSR) is a hydrogen production method recognized for its low harmful emissions and high cost-effectiveness. In this study, a three-dimensional numerical model of MSR within channels of variable cross-section. A quantitative relationship between local equilibrium constants and channel structural parameters was established based on the partial pressures of the components. Additionally, the mechanisms by which variable cross-sectional channel structural parameters regulate MSR reaction performance were quantitatively analyzed, considering fluid dynamics, hydrogen production efficiency, and chemical kinetics rates. The results indicate that the kinetic rate of MSR and local equilibrium constants are significantly influenced by the modulation of variable cross-sectional channel structural parameters, with a maximum variation of 50.6%. A positive correlation between methanol conversion rate and the local equilibrium constant of MSR was observed. Utilizing channel structural parameters to enhance MSR led to an 8.75% increase in methanol conversion rate within the same reaction volume. These conclusions may provide theoretical support for regulating volumetric reactions through variable cross-sectional channel structural parameters.

Improved photocatalytic performance of cobalt doped ZnS decorated with graphene nanostructures under ultraviolet and visible light for efficient hydrogen production

Highly dispersed Cobalt doped ZnS nanostructures were successfully fabricated on the surfaces of graphene sheets via a simple hydrothermal method. X-ray diffraction (XRD), X-ray photocurrent spectroscopy (XPS), Raman spectroscopy (RS), Fourier transform infrared spectroscopy (FTIR) and Scanning electron microscopy (SEM) were utilized to analyze the structural characteristics of the cobalt doped ZnS decorated with graphene CoxZn1-xS\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\rm Co}_x{\\rm Zn}_{1-x}{\\rm S}$$\\end{document} rGO nanostructures (NSs). UV-visible optical absorption (UV-vis) studies were conducted to investigate their optical properties. In laboratory studies utilizing water and visible light, the photocatalytic activity of CoxZn1-xS\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\rm Co}_x{\\rm Zn}_{1-x}S$$\\end{document}rGO NSs at (x = 0, 1, 2, 4 and 6 atm.%) were evaluated. Graphite Oxide (GO) was successfully transformed into sheets of graphene and CoxZn1-xSrGO\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\rm Co}_x{\\rm Zn}_{1-x}{\\rm S \\, rGO}$$\\end{document} NSs possessed a crystalline structure according to the findings of XRD, RS and FTIR analysis. SEM investigation showed graphene sheets enhanced with ZnS NSs possessed cuboidal, spheroidal form of structure and displayed a paper like appearance. UV-vis confirmed a noticeable rapid increase in transmittance along the UV wavelength area and confirmed a highly transparent NSs in the wavelength range of (180-800 nm). Calculations using density functional theory (DFT) revealed that the Co NSs have more negative conduction bands than ZnS, allowing for effective electron transfer from cobalt to ZnS and exhibiting a band gap decrease as Co content increased. The Co0.04Zn0.96S\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\rm Co}_{0.04}{\\rm Zn}_{0.96}S$$\\end{document} rGO NSs sample had the highest photocatalytic activity, measured at 7648.9μmolh-1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$7648.9 \\, \\upmu {\\rm mol} \\, {\\rm h}^{-1}$$\\end{document}. A combination of improved dispersion properties, greater surface area, increased absorption and enhanced transfer of photogenerated electrons, CoxZn1-xS\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\rm Co}_x{\\rm Zn}_{1-x}S$$\\end{document} rGO NSs increased the photocatalytic hydrogen generation activity.

Efficient hydrogen production from formic acid dehydrogenation over ultrasmall PdIr nanoparticles on amine-functionalized yolk-shell mesoporous silica

Developing heterogeneous catalysts with exceptional catalytic activity over formic acid (HCOOH, FA) dehydrogenation is imperative to employ FA as an effective hydrogen (H2) carrier. In this work, ultrasmall (1.4 nm) and well-dispersed PdIr nanoparticles (NPs) immobilized on amine-functionalized yolk-shell mesoporous silica nanospheres (YSMSNs) with radially oriented mesoporous channels have been synthesized by a co-reduction strategy. The optimized catalyst Pd4Ir1/YSMSNs-NH2 (Pd/Ir molar ratio = 4:1) exhibited a remarkable turnover frequency (TOF) of 5818 h−1 and remarkable stability at 50 °C with the addition of sodium formate (SF), resulting in complete FA conversion and H2 selectivity, exceeding most of the solid heterogeneous catalysts in previous reports under similar circumstances. Kinetic isotope effect (KIE) exploration indicates the cleavage of the CH bond is regarded as the rate-determining step (RDS) during the FA dehydrogenation process. Such excellent catalytic properties arise from the ultrafine and well-dispersed PdIr NPs supported on the nanosphere support YSMSNs-NH2, the electronic synergistic effect of PdIr alloy NPs, and the strong metal-support interaction (MSI) effect between the introduced PdIr NPs and YSMSNs-NH2 support. This work offers a new paradigm for exploiting the highly effective silica-supported Pd-based heterogeneous catalysts over the dehydrogenation of FA.

Size-modulated Pt nanoparticles for low-temperature plasmon-enhanced hydrogen production from aqueous phase reforming of methanol

Al2O3 supported Pt nanoparticles photocatalyst enables efficient hydrogen production (115.2 μmol min−1 gcat−1) through aqueous phase reforming of methanol (APRM) reaction under light irradiation at low temperatures of 150 °C, which is 6 times higher than that of APRM reaction conducted in the dark. We demonstrate that the particle size of Pt nanoparticles greatly affected the light absorption ability, which is of great importance for light utilization of the photocatalyst. The medium particle size of Pt nanoparticles enables the lower electron density states, which is benefit for the dehydrogenation of methanol and the sequential water–gas shift (WGS) reaction and eventually promoted the photocatalytic performance for hydrogen production.

Unveiling the Role of Boron on Nickel‐Based Catalyst for Efficient Urea Oxidation Assisted Hydrogen Production

AbstractUrea oxidation reaction (UOR) is an ideal alternative to oxygen evolution reaction (OER) for efficient hydrogen production but is immensely plagued by slow kinetics. Herein, a multilayer hole amorphous boron‐nickel catalyst (a‐NiBx) is fabricated through a simple chemical plating method, which displays intriguing catalytic activity toward UOR, demanding a low working potential of 1.4 V to reach 100 mA cm−2. The high performance is credited to the formation of metaborate (BO2−), which can promote the formation of high‐oxidation‐state NiOOH active phase and optimize the adsorption of urea molecules. This can be confirmed by the operando spectroscopy characteristics and density functional theory calculations. Consequently, the assembled electrolyzer utilizing NiBx as bifunctional catalysts exhibited splendid catalytic activity, requiring an evidently lower voltage of 1.66 V to reach a current density of 100 mA cm−2 and 1.57 V when using Pt/C as a cathode catalyst. Moreover, the assembled electrolyzer secured a robust stability of over 200 h, as well as a four times higher hydrogen production rate than traditional water electrolysis.

Electrocatalytic lignin oxidation for hydrogen and fine chemical co-production using platinized nickel foam in a 3D printed reactor

Biomass electrooxidation has garnered much attention in recent years, owing to its potential to circumvent greenhouse gas emissions. Substituting the sluggish water oxidation with biomass oxidizable species such as lignin at anode is thermodynamically more favorable, enabling energy efficient hydrogen production and concomitant fine chemicals. The present study shows the organosolv lignin electrooxidation in an additively manufactured 3D printed reactor (3DPR) consisting of platinized nickel foam (PtNF) as anode and cathode and compared with commercial hardware electrolyzer (CHE). The electrolysis of organosolv lignin in 3DPR outperformed CHE by achieving 1.23 times higher current at an applied voltage range from 0 to 2.2 ​V with a membrane (Nafion 115) interposed between anode and cathode under a continuous flow of lignin feed at the anode. The chronoamperometry study reveals a mixture of diverse aromatic compounds, including vanillic acid, syringic acid, 3,5-dimethoxy-4-hydroxyacetophenone, 2-hydroxyacetophenone, 4-ethycathecol, and 2,6-dimethoxyphenol in anolyte, and sinapic acid and vanillin acetate in catholyte. Thus, realizing renewable biomass electrolysis in the 3DPR is an intriguing strategy for the co-production of hydrogen and fine aromatic chemicals.

Atomically L12 ordered (PtHf)x(NiTi)100-x/CNT as bifunctional catalysts for hydrogen evolution reaction and methanol oxidation reaction with high activity and durability

Instead of a sluggish oxygen evolution reaction (OER), a methanol oxidation reaction (MOR) is combined with a hydrogen evolution reaction (HER) for efficient hydrogen production. Here, by data-driven and density functional theory (DFT) calculation, we establish a combined theoretical–and experimental strategy for designing L12 ordered structures. Based on L12-PtNiTi, Hf element is added. Hf atoms occupy the α-site (face-centered site of FCC) with Pt. Ni atoms occupy the β-site (corner site of FCC) with Ti. The (PtHf)x(NiTi)100-x nano-alloy maintains L12 structure, enhancing intrinsic anti-poisonous performance and reducing Pt content. L12 (PtHf)50(NiTi)50/CNT exhibits an overpotential of 19 mV for HER and a mass activity of 4.725 A/mgPt for MOR in acidic electrolyte. For coupling HER with MOR, the working voltage is merely 0.55 V at 10 mA cm−2. It is demonstrated by DFT calculations that ordered (PtHf)50(NiTi)50/CNT has superior electrocatalytic performance attributed to smaller H adsorption energy, stronger OH binding energy and weaker CO adsorption energy.

Isolated Octahedral Pt-Induced Electron Transfer to Ultralow-Content Ruthenium-Doped Spinel Co3O4 for Enhanced Acidic Overall Water Splitting.

The development of a highly active and stable oxygen evolution reaction (OER) electrocatalyst is desirable for sustainable and efficient hydrogen production via proton exchange membrane water electrolysis (PEMWE) powered by renewable electricity yet challenging. Herein, we report a robust Pt/Ru-codoped spinel cobalt oxide (PtRu-Co3O4) electrocatalyst with an ultralow precious metal loading for acidic overall water splitting. PtRu-Co3O4 exhibits excellent catalytic activity (1.63 V at 100 mA cm-2) and outstanding stability without significant performance degradation for 100 h operation. Experimental analysis and theoretical calculations indicate that Pt doping can induce electron transfer to Ru-doped Co3O4, optimize the absorption energy of oxygen intermediates, and stabilize metal-oxygen bonds, thus enhancing the catalytic performance through an adsorbate-evolving mechanism. As a consequence, the PEM electrolyzer featuring PtRu-Co3O4 catalyst with low precious metal mass loading of 0.23 mg cm-2 can drive a current density of 1.0 A cm-2 at 1.83 V, revealing great promise for the application of noniridium-based catalysts with low contents of precious metal for hydrogen production.

Efficient Hydrogen Production by Combined Reforming of Methane over Perovskite-Derived Promoted Ni Catalysts

Efficient Hydrogen Production by Combined Reforming of Methane over Perovskite-Derived Promoted Ni Catalysts

Oxygen vacancies promoted hydrogen production from methanol aqueous phase reforming over MgAl−LDHs supported plasmonic Ru nanoparticles catalyst

Catalytic aqueous phase reforming of methanol is a promising process for the sustainable hydrogen production. The search for highly efficient heterogeneous catalyst is a topic of interest. Herein, we report oxygen vacancies enriched MgAl−LDHs supported plasmonic Ru nanoparticles catalyst exhibit excellent photocatalytic performance for efficient hydrogen production at 150 ºC under light irradiation. Characterizations demonstrate abundant oxygen vacancies are introduced into MgAl−LDHs via “memory effect”. The local electron transfer from oxygen vacancies of the MgAl−LDHs to the Ru nanoparticles leading the formation of electron-rich Ru species, which promote the dehydrogenation of methanol under light irradiation. In situ DRIFTS demonstrated a redox mechanism of water-gas shift reaction due to the existence of oxygen vacancies, which resulted a faster hydrogen production rate. This work displays a facile strategy for synthesis of oxygen vacancies rich LDH supported metal nanoparticles catalysts and deep understanding into the pathway and mechanism toward the effective hydrogen production.

Construction of a Bi2S3/Bi0.5Na0.5TiO3 Composite Catalyst with S Vacancies for Efficient Piezo-Photocatalytic Hydrogen Production.

Photocatalytic hydrogen production with low environmental and economic costs is expected to be a powerful means to alleviate energy and environmental problems. However, how to inhibit the rapid recombination of photogenerated carriers is a challenge that photocatalytic hydrogen production has to face. In this study, the coupling of the piezoelectric effect and vacancy engineering into the photocatalytic reaction process synergistically promoted carrier separation, thereby promoting the improvement of hydrogen production performance. Specifically, the novel dual piezoelectric Bi2S3/Bi0.5Na0.5TiO3 (BS-12/BNT) piezo-photocatalyst rich in S vacancies was synthesized by an impregnation method. The hydrogen generation rate of 5% BS-12/BNT under the combined impact of light and ultrasound was up to 1019.39 μmol/g/h, which is 9.5 times higher than that of pure BNT. Various characterization analyses have confirmed that the piezoelectric-photocatalytic activity of BS/BNT composite materials is significantly improved, mainly due to the introduction of S vacancies and piezoelectric fields, which enhance the absorption of sunlight, reduce interface resistance, and so raise the photogenerated carriers' separation efficiency. In addition, the stability of BS/BNT is significantly better than that of the previously synthesized catalysts. Finally, according to the results of XPS, UV-vis, and ESR, the active groups and possible electron transfer paths generated during the piezoelectric-photocatalytic hydrogen production process were studied. This work presents a new approach to promote hydrogen production performance through the synergistic effect of the piezoelectric effect and S vacancies.

Advances in the heterostructures for enhanced hydrogen production efficiency: a comprehensive review.

The growing global energy demand and heightened environmental consciousness have contributed to the increasing interest in green energy sources, including hydrogen production. However, the efficacy of this technology is contingent upon the efficient separation of charges, high absorption of sunlight, rapid charge transfer rate, abundant active sites and resistance to photodegradation. The utilization of photocatalytic heterostructures coupling two materials has proved to be effective in tackling the aforementioned challenges and delivering exceptional performance in the production of hydrogen. The present article provides a comprehensive overview of operational principles of photocatalysis and the combination of photocatalytic and piezo-catalytic applications with heterostructures, including the transfer behavior and mechanisms of photoexcited non-equilibrium carriers between the materials. Furthermore, the effects of recent advances and state-of-the-art designs of heterostructures on hydrogen production are discussed, offering practical approaches to form heterostructures for efficient hydrogen production.

The photoelectrochemical properties of FTO/WO3/BiVO4/TiO2 photoanode for water splitting

This work investigates the photoelectrochemical performance of an FTO (Fluorine-doped Tin Oxide) /WO3 (tungsten trioxide) /BiVO4 (bismuth vanadate) /TiO2 (titanium dioxide) photoanode for water splitting. By forming a heterojunction between WO3 and BiVO4, charge separation and transportation are significantly enhanced, resulting in an improved photocurrent density. Surface modification with a thin TiO2 layer further improves the stability of the photoanode without compromising its photocurrent. The SEM, XRD, and XPS analyses confirm the successful formation of the photoanode structure. The photoelectrochemical J-V curves demonstrate that the WO3/BiVO4 composite electrode outperforms single WO3 and BiVO4 electrodes, and the TiO2 coating further enhances its performance. These findings provide valuable insights into optimizing BiVO4-based photoanodes for efficient hydrogen production via water splitting.

Gas Evolution in Water Electrolysis.

Gas bubbles generated by the hydrogen evolution reaction and oxygen evolution reaction during water electrolysis influence the energy conversion efficiency of hydrogen production. Here, we survey what is known about the interaction of gas bubbles and electrode surfaces and the influence of gas evolution on practicable devices used for water electrolysis. We outline the physical processes occurring during the life cycle of a bubble, summarize techniques used to characterize gas evolution phenomena in situ and in practical device environments, and discuss ways that electrodes can be tailored to facilitate gas removal at high current densities. Lastly, we review efforts to model the behavior of individual gas bubbles and multiphase flows produced at gas-evolving electrodes. We conclude our review with a short summary of outstanding questions that could be answered by future efforts to characterize gas evolution in electrochemical device environments or by improved simulations of multiphase flows.

Hierarchical Branched TiO2 Photo/Photoelectrocatalyst with Directed Charge Transfer for Efficient Hydrogen Production from Seawater.

The directed electron transport channel design in semiconductors, which could promote charge utilization, is attractive but rarely reported. Hierarchical branched titanium dioxide (HB-TiO2), possessing a charge cascade transfer channel, was constructed by assembling titanium-defected TiO2 nanobranches on oxygen-defected TiO2 nanobelts. The interfacial Ti/O vacancies have been detected by X-ray photoelectron and electron paramagnetic resonance spectroscopies, and the vacancies act as the "bridge" of photogenerated carrier transport. This structure maintained high photoactivity in H2 production in different mass fractions of NaCl solutions. The photocurrent density of the HB-TiO2 photoanode in natural seawater is 3.9, 2.1, and 2.6 times that of oxygen-defected TiO2 nanobelts, titanium-defected TiO2 nanobranches, and their mixture, respectively. Besides, the charge transport mechanism from the inner lattice to the TiO2 surface is proposed.