A novel double Ag@AgCl/Cu@Cu2O plasmonic nanostructure: Experimental design and LC-Mass detection of tetracycline degradation intermediates

Here a novel sunlight-driven double-plasmonic Ag^@AgCl/Cu^@Cu₂O nanophotocatalyst was constructed via photochemical-conversion and photoreduction methods for the first time. The as-prepared Ag^@AgCl/Cu^@Cu₂O was characterized by several characterizations techniques. The Scherrer equation showed the crystallite sizes of 37, 25, and 40 nm for the as-prepared Ag^@AgCl, Cu^@Cu₂O and Ag^@AgCl/Cu^@Cu₂O catalysts, while their band gap energies were 3.36, 2.51, and 3.04 eV (DRS results), respectively. TC (tetracycline) served as a probe to study its photocatalytic activity under sunlight. It was found that the as-prepared nanophotocatalyst with suitable Ag^@AgCl and Cu^@Cu₂O content not only demonstrated superior photocatalytic activity to both Ag^@AgCl and Cu^@Cu₂O plasmonic nanoparticles, but also had remarkable photostability due to the presence of two simultaneous surface plasmon resonance (SPR) in metallic Ag and Cu NPs and the hetero-junction structure formed at the interface between Ag^@AgCl and Cu^@Cu₂O. The main active species were detected through a trapping experiment which confirmed that ^?O₂^? and ^?OH were the main active species in the photocatalytic system. Central composite design (CCD) was used for the modeling and optimization of the photodegradation process. The possible photocatalytic degradation pathway of TC was proposed based on the identified intermediates. The photodegradation rate constant of TC was about 0.043 min^?1 (t_1/2 = 0.910 min) (in the range of 5–60 min). The optimum RSM run had the conditions the TC concentration of 2.0 (mg/L), Ag^@AgCl/Cu^@Cu₂O dosage of 0.53 (g/L), irradiation time 18 (min), and pH value of 6.5.     

Surface modification of the p-type Cu2ZnSnS4 photocathode with n-type zinc oxide nanorods for photo-driven salt water splitting

The sulfurization of co-sputtering Cu–Zn–Sn metal precursors was employed to prepare the quaternary copper-zinc-tin-sulphide (Cu₂ZnSnS₄, CZTS) photocathodes on substrates. Influence of [Zn]/[Sn] ratios in CZTS photocathodes on their phases, morphologies, and the efficiencies of photo-driven salt-water splitting was examined. Pristine p-type CZTS photocathodes showed the highest photo-driven performance of 0.61 mA cm^?2 in an electrolyte containing 1 M sodium chloride with the external bias kept at ?1.0 V vs. Ag/AgCl. An n-type zinc oxide (ZnO) nanorod arrays layer was then coated on the CZTS photocathode to improve its photo-driven salt-water splitting performance. The CZTS/ZnO photoelectrode had the best photo-driven performance of 1.87 mA cm^?2 in the 1 M NaCl solution under illumination with the external bias set at ?1.0 V vs. Ag/AgCl. From results of electrochemical impedance spectra measurements for the samples in the electrolyte, the CZTS/ZnO sample had good photo-driven salt-water splitting performance due to its lowest charge transfer resistance and p-n junction formed at the sample. Intensity modulated photocurrent spectroscopy and electrochemical impedance spectra results of samples indicated that the surface states at the CZTS/ZnO interface were the recombination centers with the electrons from the CZTS sample and holes from the ZnO and therefore improved its photo-driven salt-water splitting performance.     

The influence of the electrodeposition potential on the morphology of Cu2O/TiO2 nanotube arrays and their visible-light-driven photocatalytic activity for hydrogen evolution

The influence of the electrodeposition potential on the morphology of Cu₂O/TiO₂ nanotube arrays (Cu₂O/TNA) and their visible-light-driven photocatalytic activity for hydrogen evolution have been investigated for the first time in this work. The photocatalytic hydrogen evolution rate of the as-prepared Cu₂O/TNA at the deposition potential of −0.8 V was about 42.4 times that of the pure TNA under visible light irradiation. This work demonstrated a feasible and simple electrodeposition method to fabricate an effective and recyclable visible-light-driven photocatalyst for hydrogen evolution.     

Laser induced formation of copper species over TiO2 nanotubes towards enhanced water splitting performance

We proposed fast and scalable route where the ordered TiO₂ nanotubes coated with thin copper layers were annealed by the laser beam of 355 nm wavelength at different fluencies in the range of 15–120 mJ/cm². As a result, copper species are integrated with the titania substrate and the formed material exhibits unique optical absorption bands in the visible range. Moreover, X-ray photoelectron spectroscopy analysis reveals the formation of Cu₂O while the 4⁺ oxidation state of titanium is preserved. According to the electrochemical results, the material treated by laser exhibits outstanding photoelectrochemical activity comparing to the pristine titania or the one only covered by the thin copper film. In particular, when the fluence of 60 mJ/cm² was used for the modification of the titania decorated with Cu film, the current density recorded in KOH electrolyte reaches nearly 4.5 mA/cm² at +2.0 V vs. Ag/AgCl/0.1 M KCl upon visible light.     

Hairy sphere-like Ni9S8/CuS/Cu2O composites grown on nickel foam as bifunctional electrocatalysts for hydrogen evolution and urea electrooxidation

The urea solution electrolysis has become more attractive than water splitting, because it not only produces clean H₂ via the cathodic hydrogen evolution reaction (HER) with lower cell voltage, but also treats sewage containing urea through anodic urea oxidation reaction (UOR). However, lack of efficient electrocatalysts for HER and UOR has limited its development. Herein, hairy sphere -like Ni₉S₈/CuS/Cu₂O composites were synthesized on nickel foam (NF) in situ by a two-step hydrothermal method. The Ni₉S₈/CuS/Cu₂O/NF exhibited good electrocatalytic activity for both HER (?0.146 V vs. RHE to achieve 10 mA cm^?2) and UOR (1.357 V vs. RHE to achieve 10 mA cm^?2). Based on the bifunctional properties of Ni₉S₈/CuS/Cu₂O/NF, a dual-electrode urea solution electrolytic cell was constructed, which only needed a low voltage of 1.47 V to reach a current density of 10 mA cm^?2, and displayed a good stability during a 20-h test. In addition, the reason for the good catalytic activity of Ni₉S₈/CuS/Cu₂O/NF was analyzed and the UOR mechanism was discussed in detail. Our research shows that Ni₉S₈/CuS/Cu₂O/NF is a very promising low-cost dual-function electrocatalyst, which can be used for high-efficiency electrolysis of urea solution to produce hydrogen and treat wastewater.     

Preparation and enhanced photoelectrocatalytic properties of a three-dimensional TiO2-Au porous structure fabricated using superaligned carbon nanotube films

Three dimensional TiO₂–Au cross-nanoporous structure (3D TiO₂–Au CNS) as an efficient photoelectrocatalytic system was fabricated using superaligned carbon nanotube films as etching masks and electron-beam evaporation. The 3D TiO₂–Au CNS exhibited a broad absorption band in the visible region, and the incident photon-to-current conversion efficiency of 3D TiO₂–Au CNS/Ti electrode was 3–4 times higher than that of pure TiO₂ electrode. The photocurrent density of the 3D TiO₂–Au CNS device was 0.079 mA cm⁻² at 0 V vs. Ag/AgCl with a solar irradiance of 100 mW cm⁻². This developed preparation method was simple, of high flexibility and can be adopted for mass production due to its low cost and good compatibility with other processing technologies. The 3D TiO₂–Au CNS and its preparation method have important value in design of photoelectrocatalytic system for research and practical applications, which may have a potential utility in photocatalytic and other photoelectrocatalytic reactions.     

H2 evolution from a photoelectrochemical cell with n-Cu2O photoelectrode under visible light irradiation

H₂ evolution was observed for the first time from a photoelectrochemical cell using an n-type Cu₂O photoelectrode under visible light irradiation. Three-electrode configuration was used in the photoelectrochemical cell to observe H₂ evolution. AgCl/Ag calomel electrode and a platinum plate were used as the reference and counter electrodes, respectively. Fe²⁺/Fe³⁺ redox couple was used as the electrolyte. H₂ evolution was visible on the platinum electrode in the photoelectrochemical cell.     

Effect of alkaline-doping on photoelectrochemical activity of electrodeposited cuprous oxide films

P-type Cu₂O films with alkaline ions (Li⁺, Na⁺ and K⁺) of unintentional dopants on indium tin oxide coated glass substrate are successfully fabricated via a simple electrodeposition method for photoelectrochemical (PEC) hydrogen generation. The SEM and XRD analysis show the as-grown films with the pyramid-like morphology and cubic structure, and the composition of alkaline-doped Cu₂O films are examined using XPS spectroscopy to demonstrate the substitution of alkaline ions in the Cu₂O lattice. The optical analyses, including the absorbance and low-temperature photoluminescence spectra, confirm a bandgap of 2.3 eV and the presence of structural defects in alkaline-doped Cu₂O films. The Mott-Schottky plot shows the flat band potentials of the alkaline-doped Cu₂O films to be approximately ?0.1 V and the hole concentrations in the order of 10¹⁷ cm^?3. Significantly, the Cu₂O:Li film photocathode exhibits a higher photocurrent of ?2.2 mA cm^?2 at a potential of ?0.6 V vs Ag/AgCl which are greater than those of Cu₂O:K and Cu₂O:Na films due to greater preferred orientation degrees along (111) and less structural defects, because the ionic radii of Cu and Li is similar. These results demonstrate the great potential of alkaline doped Cu₂O films in solar-related applications.     

Oxygen vacancy-engaged interfacial charge transfer modulation for upgrade Rh-catalyzed hydrogen and oxygen productions

Developing efficient modulation strategies to upgrade the catalytic activity and reusability of Rh-catalyzed hydrogen evolution from ammonia borane (AB) hydrolysis are definitely profitable but remains a grand challenge. Here, we develop a stepwise activation strategy to produce highly active and reusable Rh/CoFe₂O₄-SB-H₂ with abundant oxygen vacancies and strong electronic metal-support interaction through stepwise reduction of Rh/CoFe₂O₄ precursor using sodium borohydride and H₂ as the reducing agents. Under ultrasonic irradiation, Rh/CoFe₂O₄-SB-H₂ with an ultralow Rh loading of 0.20 wt% can be utilized as an excellent catalyst for hydrogen production from room-temperature AB hydrolysis with a high turnover frequency (TOF) of 1894 min⁻¹. The TOF value could be further promoted to 15,570 min⁻¹ in the alkaline ultrasonic environment. The catalyst has a superior reusability with 75% maintaining activity of initial one in the 10^th cycle. The strong electronic metal-support interaction, rich oxygen vacancies and ultrasound irradiation promote the oxidative cleavage of the O–H bonds in attracted H₂O and thus account for high performance toward hydrogen production from AB. This catalyst can also be utilized as an active catalyst for oxygen generation from H₂O₂ decomposition. The developed strategies can be applied to upgrade the performance of other reducible metal oxides supported metal catalysts toward catalytic applications.     

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.     

Silver/titania nanocomposite-modified photoelectrodes for photoelectrocatalytic methanol oxidation

Silver deposited titania (Ag/TiO₂) nanocomposite thin films were fabricated by the simple sonochemical deposition of Ag on preformed aerosol-assisted chemical vapor deposited TiO₂ thin films. The photelectrocatalytic performance of a newly fabricated Ag/TiO₂-modified photoelectrode was studied for methanol oxidation under simulated solar AM 1.5G irradiation (100 mW/cm²). The Ag/TiO₂-modified photoelectrode showed a photocurrent density of 1 mA/cm², which is four times that of an unmodified TiO₂ photoelectrode. The modification of Ag on the TiO₂ surface significantly enhanced the photoelectrocatalytic performance by improving the interfacial charge transfer processes, which minimized the charge recombination. Density functional theory (DFT) calculation studies revealed that methanol could be easily adsorbed onto the Ag surfaces of Ag/TiO₂ via a partial electron transfer from Ag to methanol. The newly fabricated Ag/TiO₂-modified photoelectrode could be a promising candidate for photoelectrochemical applications.     

An efficient tandem photoelectrochemical cell composed of FeOOH/TiO2/BiVO4 and Cu2O for self-driven solar water splitting

An integrated solar water splitting tandem cell without external bias was designed using a FeOOH modified TiO₂/BiVO₄ photoanode as a photoanode and p-Cu₂O as a photocathode in this study. An apparent photocurrent (0.37 mA/cm² at operating voltage of +0.36 V_RHE) for the tandem cell without applied bias was measured, which is corresponding to a photoconversion efficiency of 0.46%. Besides, the photocurrent of FeOOH modified TiO₂/BiVO₄–Cu₂O is much higher than the operating point given by pure BiVO₄ and Cu₂O photocathode (∼0.07 mA/cm² at +0.42 V_RHE). Then we established a FeOOH modified TiO₂/BiVO₄–Cu₂O two-electrode system and measured the current density-voltage curves under AM 1.5G illumination. The unassisted photocurrent density is 0.12 mA/cm⁻² and the corresponding amounts of hydrogen and oxygen evolved by the tandem PEC cell without bias are 2.36 μmol/cm² and 1.09 μmol/cm² after testing for 2.5 h. The photoelectrochemical (PEC) properties of the FeOOH modified TiO₂/BiVO₄ photoanode were further studied to demonstrate the electrons transport process of solar water splitting. This aspect provides a fundamental challenge to establish an unbiased and stabilized photoelectrochemical (PEC) solar water splitting tandem cell with higher solar-to-hydrogen efficiency.     

Highly efficient sputtered Ni-doped Cu2O photoelectrodes for solar hydrogen generation from water-splitting

Hydrogen gas can be converted to electricity through fuel cells and is considered as a friendly energy source. Herein, pure Cu₂O and Ni-doped Cu₂O thin films were deposited on glass substrates using the RF/DC-sputtering technique for hydrogen production via the photoelectrochemical (PEC) water-splitting process. The preferred orientation for pure and Ni-doped Cu₂O films was (111) crystallographic plane. The average nanograins size was decreased from 32.17 nm for pure to 10.40 nm through the doping process with Ni content. Field-emission scanning electron microscopy (FE-SEM) and ImageJ analysis showed that the pure Cu₂O and Ni-doped Cu₂O were composed of normal distribution of nanograins in a regular form. The optical bandgap of the Cu₂O film was decreased from 2.35 eV to 1.9 eV after doping with 2.6 wt% of Ni-dopants. The photoluminescence (PL) spectra for all the sputtered films were recorded at room temperature to examine the effect of Ni-dopants in the Cu₂O lattice. Pure and Ni-doped Cu₂O films were applied for PEC water splitting for hydrogen (H₂) production under white light and monochromatic illumination. The PEC studies displayed that increasing the Ni content up to 2.6 wt% in the pure Cu₂O films led to an increase in the photocurrent density to reach ?5.72 mA/cm². The optimum photoelectrode was studied for reproducibility, stability, and electrochemical impedance. The incident photon to current conversion efficiency (IPCE%) was 16.35% at 490 nm, and the applied bias photon to current conversion efficiency (ABPE%) was 0.90% at 0.65 V. Consequently, Ni-doped Cu₂O photoelectrodes are efficient and low-cost for practical and industrial solar H₂ production.     

Photocurrent and photoelectrochemical hydrogen production with tin porphyrin and platinum nanowires immobilized with nafion on glassy carbon electrode

Platinum nanowires mixed with Tin meso-tetra (4-pyridyl) porphine dichloride and nafion solution was used to modify the surface of glassy carbon electrode for photocurrent generation and photo-electrochemical hydrogen production. Different concentrations of porphyrin (50 μM, 100 μM, 300 μM and 500 μM) and platinum loading (200 μg/cm², 400 μg/cm², 600 μg/cm² and 800 μg/cm²) were tested at −150 mV Vs Ag/AgCl in reaction cell containing the modified glassy carbon electrode as working electrode, platinum wire as counter electrode and Ag/AgCl as reference electrode, under illumination to determine the optimum, based on photocurrent production in 50 mM potassium hydrogen phthalate buffer (pH 3) containing 0.1Na₂SO₄ as supporting electrolyte. Optimum photocurrent was obtained at 100 μM tin porphyrin and 600 μg/cm² platinum loading. Detectable amount of hydrogen was produced at −350 mV Vs Ag/AgCl under irradiation with visible light.     

Metal (oxide) modified (M= Pd,Ag, Au and Cu) H2SrTa2O7 for photocatalytic CO2 reduction with H2O: The effect of cocatalysts on promoting activity toward CO and H2 evolution

Ag, Pd, Au, Cu₂O as cocatalysts were loaded on the layered H₂SrTa₂O₇ (HST) for photocatalytic CO₂ reduction with H₂O. The characterization revealed that cocatalysts loaded on the surface of HST can effectively promote the separation of photogenerated electrons and holes due to the formation of Schottky barrier or p-n junction, thus enhancing photocatalytic activity. Of note, Ag, Pd, Au, Cu₂O loading exhibited obviously different performance on promoting photocatalytic activity of HST toward CO evolution and H₂ evolution because of the different overpotentials of CO evolution and H₂ evolution on loaded photocatalysts. Cocatalysts with low overpotentials of CO or H₂ evolution act as active sites for CO or H₂ evolution, thus controlling the selectivity toward CO or H₂. The Au/HST exhibited high activity for only H₂ evolution (17.5 μmol g⁻¹ h⁻¹) due to relative low overpotential for H₂ evolution (0.67 V) while the Cu₂O/HST exhibited high activity only for CO evolution (0.23 μmol g⁻¹ h⁻¹) due to relative low overpotential for CO evolution (0.40 V). The Pd/HST sample exhibits high photocatalytic activity for both CO and H₂ evolution rates due to the low overpotential for CO and H₂ evolution, reaching 4.0 and 4.7 times of bare HST, respectively. This work here gives an in-depth understanding of the effect of cocatalysts on promoting photocatalytic activity and selectivity and can also give guidance to design photocatalysts with high activity and selectivity for photocatalytic CO₂ reduction with H₂O.     

Syngas production through CH4-assisted co-electrolysis of H2O and CO2 in La0.8Sr0.2Cr0.5Fe0.5O3-δ-Zr0.84Y0.16O2-δ electrode-supported solid oxide electrolysis cells

High temperature co-electrolysis of H₂O/CO₂ allows for clean production of syngas using renewable energy, and the novel fuel-assisted electrolysis can effectively reduce consumption of electricity. Here, we report on symmetric cells YSZ-LSCrF | YSZ | YSZ-LSCrF, impregnated with Ni-SDC catalysts, for CH₄-assisted co-electrolysis of H₂O/CO₂. The required voltages to achieve an electrolysis current density of ?400 mA·cm^?2 at 850 °C are 1.0 V for the conventional co-electrolysis and 0.3 V for the CH₄-assisted co-electrolysis, indicative of a 70% reduction in the electricity consumption. For an inlet of H₂O/CO₂ (50/50 vol), syngas with a H₂:CO ratio of ≈2 can be always produced from the cathode under different current densities. In contrast, the anode effluent strongly depends upon the electrolysis current density and the operating temperature, with syngas favorably produced under moderate current densities at higher temperatures. It is demonstrated that syngas with a H₂:CO ratio of ≈2 can be produced from the anode at a formation rate of 6.5·mL min^?1·cm^?2 when operated at 850 °C with an electrolysis current density of ?450 mA·cm^?2.     

Pentadentate Copper(II)-amidate complex as a precatalyst for electrocatalytic proton reduction

Electrochemical reduction studies of a mononuclear Cu(II) complex bearing a pentadentate amidate ligand under both aqueous and non-aqueous media revealed the deposition of a heterogeneous film on the electrode. The heterogeneous film was grown on an FTO working electrode by control potential electrolysis (CPE) at ?0.9 V vs. NHE for 3 h (pH 3.0, phosphate buffer). Characterization of the electrodeposited film by SEM, EDX and XPS indicates the preferential formation of Cu₂O. The FTO/Cu₂O cathode, thus formed, exhibits electrocatalytic proton reduction in acidic aqueous medium (pH 3.0) with 95% Faradaic efficiency at moderate overpotential (η = 320 mV at onset). The overpotential required to reach 1 mA/cm² is 530 mV. The FTO/Cu₂O cathode maintained a current density of 2.5 mA cm^?2 for a period of 3 h and showed stability after 200 scan cycles.     

A novel photoelectrochemical cell with self-organized TiO2 nanotubes as photoanodes for hydrogen generation

A photoelectrochemical (PEC) cell with an innovative design for hydrogen generation via photoelectrocatalytic water splitting is proposed and investigated. It consisted of a TiO₂ nanotube photoanode, a Pt/C cathode and a commercial asbestos diaphragm. The PEC could generate hydrogen under ultraviolet (UV) light-excitation with applied bias in KOH solution. The Ti mesh was used as the substrate to synthesize the self-organized TiO₂ nanotubular array layers. The effect of the morphology of the nanotubular array layers on the photovoltaic performances was investigated. When TiO₂ photocatalyst was irradiated with UV-excitation, it prompted the water splitting under applied bias (0.6 V vs. Normal Hydrogen Electrode, NHE.). Photocurrent generation of 0.58 mA/cm² under UV-light irradiation showed good performance on hydrogen production.     

Investigation of Photo(electro)catalytic water splitting to evolve H2 on Pt-g-C3N4 nanosheets

g-C₃N₄ has shown great potentials in photocatalytic water splitting to produce hydrogen. Herein, we successfully synthesized g-C₃N₄ nanosheets via exfoliating bulk g-C₃N₄. And different metal nanoparticles were photo-deposited onto the surface of g-C₃N₄ nanosheets. The photocatalytic H₂ production activity of g-C₃N₄ nanosheets increased from 0 to 11.2 μmol/h/g_cat. The Pt loaded g-C₃N₄ nanosheets manifested the highest H₂ production activity with a rate of 589.4 μmol/h/g_cat. In addition, the hydrogen evolution rate was further enhanced with addition of external bias to fabricate a photoelectrocatalytic (PEC) system. And the maximum hydrogen production rate (23.1 mmol/h/m²) was obtained at a voltage of 0.6 V (vs. Ag/AgCl). The enhancement in H₂ production may be due to the following reasons: (1) Two-dimensional atomic flakes is beneficial to increase the specific surface area of g-C₃N₄, enhance the mobility of carriers, and improve the energy band structure, (2) Pt nanoparticles play an important role in g-C₃N₄ electron transport, (3) the g-C₃N₄ nanosheets loaded with Pt nanoparticles exhibited significant enhancement in photoelectrocatalytic performance, which may be attributed to its enhanced electronic conductivity and photoelectrochemical surface area, (4) Pt inhibited the recombination of photogenerated carriers and significantly improved the photocatalytic performance. The enhancement mechanism was deeply discussed and explained in this work.     

Mechanistic implications of the solvent kinetic isotope effect in the hydrolysis of NaBH4

The sodium borohydride, NaBH₄, hydrolysis mechanism is studied via the H₂O/D₂O kinetic isotope effect (KIE). This reaction is of importance as NaBH₄ is considered as a hydrogen storage material. Nowadays, hydrogen is thought to be one of the most promising and efficient clean energy carriers. In order to control the rate of the hydrogen evolution reaction (HER), one has to understand the mechanism of its production. The H₂O/D₂O KIE of the reactions of NaBH₄ and NaBD₄ with water was studied in solutions containing a ratio of H₂O/D₂O = 1.00. The separation factor, α, of both reactions is α = 5.0 ± 1.0. The rate of the hydrolysis of BD₄^? in H₂O is faster than that of BH₄^?. The results point out that the rate-determining step in all hydrolysis stages is the H–OH bond scission.