Water Oxidation Kinetics Research Articles

Tailoring Carrier Dynamics of BiVO4 Photoanode via Dual Incorporation of Au and Co(OH)x Cooperative Modification for Photoelectrochemical Water Splitting

AbstractPhotoelectrochemical solar to hydrogen production is a promising way to achieve carbon neutrality, but severe charge recombination in photoanodes limits the conversion efficiency. Herein, Au nanoparticles and Co(OH)x co‐sensitized bismuth vanadate (BiVO4) to construct AuCo(OH)x/BiVO4 photoanode for significantly enhancing the performance of photoelectrochemical water splitting. This process significantly improves the bulk charge carrier separation efficiency, the surface kinetics of water oxidation, and the electron density of BiVO4 photoanode through Au surface plasmon resonance (SPR) and Co(OH)x oxygen evolution catalysts effect. Additionally, the enhancement of the *O and the *OOH generation accelerate the oxygen evolution reaction kinetics. Consequently, the constructed AuCo(OH)x/BiVO4 photoanode demonstrates an excellent photocurrent of 6.2 mA cm−2 at 1.23 V versus reversible hydrogen electrode and a stable continuous output within 42 h. This work contributes to developing high‐efficiency and high‐stability photoanodes for solar H2 production through SPR effect and oxygen evolution catalysts.

Boosting Photoelectrochemical Water Oxidation Performance of Ti–Fe2O3 Photoanode via NH2–MIL–53(FeCo) as a Cocatalyst

α–Fe2O3 is a promising photoanode that can be used for solar‐driven photoelectrochemical (PEC) water splitting. However, due to low carrier separation efficiency and slow water oxidation kinetics, the PEC performance of Ti–Fe2O3 is still severely hindered. Here, a novel inorganic–organic hybrid composite photoanode is prepared by depositing NH2–materials of institute Lavoisier (MIL)–53(FeCo) cocatalyst on the surface of Ti–Fe2O3 using solvothermal method. In the results, it is shown that the Ti–Fe2O3/NH2–MIL–53(FeCo) photoanode has a high photocurrent density (3.0 mA cm−2 at 1.23 V vs reversible hydrogen electrode (RHE), which is 5.1 times that of bare Ti–Fe2O3, and the initial potential of water oxidation also undergoes a negative change of about 100 mV. The separation efficiency of Ti–Fe2O3/NH2–MIL–53(FeCo) is significantly enhanced, and the charge injection efficiency increases from 17.6% to 68% at 1.23 V versus RHE. In the further research, it is suggested that the excellent PEC performance of Ti–Fe2O3/NH2–MIL–53(FeCo) may be attributed to an increase in carrier density, prolonged carrier recombination time, and an increase in exposed reactive sites. In this study, a new understanding for the design of Ti–Fe2O3 photoanodes with superior PEC performance based on metal organic framework modification is provided.

Photocatalytic Overall Water Splitting with a Solar-to-Hydrogen Conversion Efficiency Exceeding 2 % through Halide Perovskite.

Photocatalytic water splitting using semiconductors is a promising approach for converting solar energy to clean energy. However, challenges such as sluggish water oxidation kinetics and limited light absorption of photocatalyst cause low solar-to-hydrogen conversion efficiency (STH). Herein, we develop a photocatalytic overall water splitting system using I3 -/I- as the shuttle redox couple to bridge the H2-producing half-reaction with the O2-producing half-reaction. The system uses the halide perovskite of benzylammonium lead iodide (PMA2PbI4, PMA=C6H5CH2NH2) loaded with MoS2 (PMA2PbI4/MoS2) as the H2 evolution photocatalyst, and the RuOx-loaded WO3 (WO3/RuOx) as the O2 evolution photocatalyst, achieving a H2/O2 production in stoichiometric ratio with an excellent STH of 2.07 %. This work provides a detour route for photocatalytic water splitting with the help of I3 -/I- shuttle redox couple in the halide perovskite HI splitting system and enlightens one to integrate and utilize multi catalytic strategies for solar-driven water splitting.

Photocatalytic Overall Water Splitting with a Solar‐to‐Hydrogen Conversion Efficiency Exceeding 2 % through Halide Perovskite

AbstractPhotocatalytic water splitting using semiconductors is a promising approach for converting solar energy to clean energy. However, challenges such as sluggish water oxidation kinetics and limited light absorption of photocatalyst cause low solar‐to‐hydrogen conversion efficiency (STH). Herein, we develop a photocatalytic overall water splitting system using I3−/I− as the shuttle redox couple to bridge the H2‐producing half‐reaction with the O2‐producing half‐reaction. The system uses the halide perovskite of benzylammonium lead iodide (PMA2PbI4, PMA=C6H5CH2NH2) loaded with MoS2 (PMA2PbI4/MoS2) as the H2 evolution photocatalyst, and the RuOx‐loaded WO3 (WO3/RuOx) as the O2 evolution photocatalyst, achieving a H2/O2 production in stoichiometric ratio with an excellent STH of 2.07 %. This work provides a detour route for photocatalytic water splitting with the help of I3−/I− shuttle redox couple in the halide perovskite HI splitting system and enlightens one to integrate and utilize multi catalytic strategies for solar‐driven water splitting.

Self-Etching Synthesis of Superhydrophilic Iron-Rich Defect Heterostructure-Integrated Catalyst with Fast Oxygen Evolution Kinetics for Large-Current Water Splitting.

Developing catalysts with rich metal defects, strong hydrophilicit, and extensive grain boundaries is crucial for enhancing the kinetics of electrocatalytic water oxidation and facilitating large-current water splitting. In this study, we utilized pH-controlled etching and gas-phase phosphating to synthesize a flower-like Ni2P-FeP4-Cu3P modified nickel foam heterostructure catalyst. This catalyst features pronounced hydrophilicity and a high concentration of Fe defects. It exhibits low overpotentials of 156 mV and 210 mV at current densities of 10 and 100 mA cm-2 respectively, and maintains stability for up to 200 h at 100 mA cm-2 with only 7.3% degradation, showcasing outstanding electrocatalytic water oxidation performance. Furthermore, when integrated into a Ni2P-FeP4-Cu3P/NF||Pt-C/NF electrolyzer, it achieves excellent overall water splitting performance, reaching current densities of 10 and 400 mA cm-2 at just 1.47 V and 1.73 V, respectively, and operates stably for 60 h at 500 mA cm-2 with minimal degradation. Analysis indicates that high-valence oxyhydroxides/phosphides of Ni, Fe, and Cu act as the primary active species. The presence of abundant Fe defects enhances electron transfer, strong hydrophilicity improves electrolyte contact, and numerous grain boundaries synergistically modulate the activation energy between active sites and oxygen-containing intermediates, significantly improving the kinetics of water oxidation.

Nickel-doped and surface fluorinated tungsten trioxide photoanode with enhanced photoelectrochemical water oxidation

To improve the slow charge transfer and high electron-hole recombination rate of tungsten trioxide (WO3), a nickel-doped and surface fluorinated WO3 photoanode is proposed. Compared with the unmodified and one-step modified WO3 photoanodes, the co-modified F/Ni-WO3 with two steps exhibits superior photoelectrochemical (PEC) performance with a significantly high photocurrent density of 1.03 mA/cm2 compared to 0.51 mA/cm2 of bare WO3 at 1.23 V vs. RHE. Ni doping can accelerate the kinetics of water oxidation and extend the light absorption range of the WO3 photoanode, while surface fluorination can enhance the surface electronegativity and hydrophilicity of the WO3 photoanode. The synergistic influence of the Ni doping and surface fluorination results in a lower carrier transport impedance, higher charge separation efficiency and larger electrochemically active surface of the WO3 photoanode which eventually contribute to the enhanced PEC performance for water oxidation.

In-situ synthesis of Fe phosphate layer on the porous hematite nanocube for efficient photoelectrochemical water splitting

Hematite (α-Fe2O3) is considered as an ideal photoanode material in photoelectrochemical (PEC) water splitting system due to its suitable band gap, excellent stability and abundant reserves. However, the actual PEC water oxidation performance of α-Fe2O3 is greatly limited by its severe charge recombination and sluggish water oxidation kinetics. Here, an in-situ generated Fe phosphate (Fe-Pi) coating strategy is applied on the surface of porous hematite nanocube (Fe2O3 NC) to realize PEC water oxidation effectively. The obtained Fe-Pi/Fe2O3 NC photoanode exhibits a remarkable PEC property with a photocurrent density of 2.7mAcm-2 at 1.23V vs. RHE, which was about 5.7-fold enlarged compared to the pristine nanorod-like hematite (Fe2O3 NR) photoanode. Detailed studies have shown that the porous Fe2O3 NC possesses an enhanced ability in light absorption and charge separation than the traditional Fe2O3 NR photoanode. In addition, the in-situ loading of Fe-Pi layer as a co-catalyst can not only effectively passivate the surface trapping states of Fe2O3 NC and suppress interfacial charge recombination, but also quickly extract the holes to participate in the water oxidation reaction. Our study suggests that the further surface modification based on morphological engineering is an effective strategy to improve the PEC performance of hematite.

Fe-N Co-Doped BiVO4 Photoanode with Record Photocurrent for Water Oxidation.

Bismuth vanadate ranks among the most promising photoanodes for photoelectrochemical water splitting. Nonetheless, slow charge separation and transportare key barriers to its photoefficiency. Here, we present a co-doping strategy that significantly improves the charge separation performance of BVO. Under standard one sun illumination, the Fe-N co-doped BVO photoanode (Fe-N-BVO) by N-coordinated Fe precursor reaches a record photocurrent density of 7.01 mA cm-2 at 1.23 V vs RHE after modified a surface co-catalyst. By contrast, much lower photocurrent density is obtained for the N-doped and Fe-doped BVO with separated N and Fe precursors. The detailed characterizations show that the high activity of the Fe-N-BVO is attributed to the enhanced photo-induced bulk charge separation and the accelerated surface water oxidation kinetics. XPS, EXAFS and DFT calculations clearly show that, instead of formation of deep trapping state in the individually doped BVO, the co-doping of Fe-N into BVO generates Fe-based electronic states just below the bottom of conduction band and N-derived states just above the top of valence band. Such modulations in electronic structure enable the efficient trap of the electrons and holes to enhance the separation of photo-induced carriers, but hinder the charge recombination originated from the deep trapping sites.

Enhancing the photoelectrochemical performance of TiO2 photoanode by employing carbon nanoparticles as electron reservoirs and photothermal materials.

Photoelectrochemical (PEC) water splitting is regarded as a potential technique for converting solar energy. However, the fast charge recombination and slow water oxidation kinetics significantly have hindered its practical application. It is found that an elevation in operation temperature can activate the charge transport in the photoanodes. Here, a strategy was performed that carbon nanoparticles were employed to TiO2 nanorods, acting as electron reservoirs as well as photothermal materials. More specifically, a record photocurrent density of 1.62mAcm-2 at 1.23V vs. RHE has been achieved, accompanied by a high charge separation efficiency of 96% and a long-term durability for 8h. The detailed experimental results reveal that under NIR light irradiation, the synergistic effect between electron storage and temperature rise leads to accelerated charge transport in the bulk and water oxidation kinetics on the surface. This research offers a new perspective on how to boost the PEC performance of photoelectrodes.

Promoting effect of interfacial hole accumulation on photoelectrochemical water oxidation in BiVO4 and Mo-doped BiVO4

Hole transfer at the semiconductor-electrolyte interface is a key elementary process in (photo)electrochemical (PEC) water oxidation. However, up to now, a detailed understanding of the hole transfer and the influence of surface hole density on PEC water oxidation kinetics is lacking. In this work, we propose a model for the first time in which the surface accumulated hole density in BiVO4 and Mo-doped BiVO4 samples during water oxidation can be acquired via employing illumination-dependent Mott-Schottky measurements. Based on this model, some results are demonstrated as below: (1) Although the surface hole density increases when increasing light intensity and applied potential, the hole transfer rate remains linearly proportional to surface hole density on a log-log scale. (2) Both water oxidation on BiVO4 and Mo-doped BiVO4 follow first-order reaction kinetics at low surface hole densities, which is in good agreement with literature. (3) We find that water oxidation active sites in both BiVO4 and Mo-doped BiVO4 are very likely to be Bi5+, which are produced by photoexcited or/and electro-induced surface holes, rather than VOx species or Mo6+ due to their insufficient redox potential for water oxidation. (4) Introduction of Mo doping brings about higher OER activity of BiVO4, as it suppresses the recombination rate of surface holes and increases formation of Bi5+. This surface hole model offers a general approach for the quantification of surface hole density in the field of semiconductor photoelectrocatalysis.

Enhanced charge carrier separation and stable photoelectrochemical water splitting via a high-performance BiVO4/BiOBr Type-II heterojunction

The development of an ideal photoanode that exhibits broad light absorption, efficient photogenerated carrier separation, and superior transmission efficiency remains a pivotal challenge in enhancing the sluggish photoelectrochemical (PEC) water splitting reaction. Here, we present an efficacious strategy to bolster the PEC performance of oxygen evolution by fabricating a BiVO4/BiOBr heterojunction through a combined electrochemical deposition-calcination approach and the successive ionic layer adsorption and reaction (SILAR) method. The band structure of BiOBr is optimally aligned with BiVO4, enabling the heterojunction to significantly enhance the separation efficiency of photogenerated charges and accelerate the kinetics of PEC water oxidation. Under simulated sunlight irradiation, the BiVO4/BiOBr heterojunction exhibits a remarkable photocurrent density of 2.69 mA/cm2 at 1.23 V vs. reversible hydrogen electrode (RHE), surpassing the performance of bare BiVO4 film (0.46 mA/cm2 at 1.23 V vs. RHE) and demonstrating exceptional stability. This work offers novel insights into the rational design and fabrication of solar-driven PEC water splitting photoanodes.

An efficient hole transport layer and novel citrate-FeCo(OH)x cocatalyst co-modified Ti-Fe2O3 photoanode towards boosting photoelectrochemical water oxidation

The restricted performance of α-Fe2O3 in photoelectrochemical (PEC) water splitting is currently constrained by the slow kinetics of water oxidation and the rapid charge recombination. Herein, we prepared a composite photoanode with molecular copper phthalocyanine (CuPc) as the hole transport layer and citric acid assisted FeCo(OH)x as the cocatalyst using a simple two-step method. The optimized Ti-Fe2O3/CuPc/citrate-FeCo(OH)x photoanode achieved an photocurrent density of 2.67 mA/cm−2 at 1.23 V vs. RHE, which is 6.5 times higher than pure Ti-Fe2O3 and can maintain long-term stability. Detailed studies have shown that CuPc and Ti-Fe2O3 can form an interface electric field for hole oriented transport, significantly improving the transfer of photogenerated carriers. The FeCo(OH)x coating assisted by citric acid deposition not only forms a conformal coating, but also acts as a bifunctional layer to quickly transfer holes from Ti-Fe2O3/CuPc to the electrolyte. It also significantly increases the reactive active sites and hydrophilicity of Ti-Fe2O3/CuPc, which further accelerates the water oxidation kinetics. This study provides a promising strategy for the development of an efficient and cost-effective photoanode and extends the design concept of a PEC water splitting device.

SnS2 Nanoparticles Embedded in BiVO4 Surfaces via Eutectic Decomposition for Enhanced Performance in Photoelectrochemical Water Splitting.

BiVO4 has garnered substantial interest as a promising photoanode material for photoelectrochemical water-splitting due to its narrow band gap and appropriate band edge positions for water oxidation. Nevertheless, its practical use has been impeded by poor charge transport and sluggish water oxidation kinetics. Here, a hybrid composite photoanode is fabricated by uniformly embedding SnS2 nanoparticles near the surface of a BiVO4 thin film, creating a type II heterostructure with strong interactions between the nanoparticles and the film for efficient charge separation. This structure forms via eutectic melting during atomic layer deposition of SnS2 with subsequent phase separation between SnS2 and BiVO4 at room temperature, offering greater advantages and flexibilities over conventional exsolution techniques. Furthermore, the SnS2/BiVO4 hybrid composite is coated with a thin amorphous ZnS passivation layer to accelerate charge transfer process and enhance long-term stability. The optimized BiVO4/SnS2/ZnS photoanode exhibits a photocurrent density of 5.44mAcm-2 at 1.23V versus RHE, which is 2.73 times higher than that of the BiVO4 photoanode, and a dramatic improvement in photostability retention at 1.23V versus RHE, increasing from 55% to 91% over 24 hours. This method of anchoring nanoparticles onto host materials proves highly valuable for energy and environmental applications.

Recrystallization reduces surface oxygen vacancies to unlock hole transfer channel for hematite photoelectrochemistry

Hematite is a promising photoanode in photoelectrochemical water splitting system, but the slow water oxidation kinetics at the photoanode/electrolyte interface seriously limits the photoelectrochemical properties. Improving the surface state of hematite is an effective method to improve the transport and separation of carriers. Herein, we propose a strategy to recrystallize the hematite, which can effectively reduce the oxygen vacancies on the surface of hematite, increase active sites and improve the oxidation activity of water. The experimental results show that the charge recombination rate of the recrystallized Fe2O3 photoanode is reduced, and the carrier transport efficiency is improved. The photocurrent density at 1.23 V is four times higher than that of the original hematite, and the initial potential shifts negatively by about 20 mV, which is attributed to the upward bending of hematite energy band and the reduction of surface defects after treatment. This research provides a feasible strategy for designing efficient α-Fe2O3 photoanode.

Photoelectrochemical Water Splitting: A Visible-Light-Driven CoTiO3@g-C3N4-Based Photoanode Interface Follows the Type II Heterojunction Scheme.

Harnessing solar energy can be efficiently used to generate hydrogen by photochemical water splitting, which is a sustainable and environmentally benign energy source. Here, a unique visible-light-driven CoTiO3@g-C3N4 (CTOCN)-based photoanode interface has been optimized and developed with modification to follow the type II heterojunction for the enhancement of photoelectrochemical water splitting. Initially, a graphitic carbon nitride-loaded CoTiO3 (with 10 wt % g-C3N4) composite was obtained using a one-pot solvothermal method. Accordingly, the type II heterojunction interface between g-C3N4 and CoTiO3 has been successfully created and confirmed by the acquired phase, morphological, and optical examinations. Thereby, heterostructure generations with interfacial interaction were enabled to decrease photogenerated electron-hole pair recombination, leading to enhanced charge transfer for water oxidation kinetics. The minimal charge transfer resistance and hole relaxation lifetime (p) shown in Nyquist and Bode plots have further confirmed the rapid electron transport across the electrode/electrolyte interfaces, which is attributed to an enhanced absorption of holes for the water splitting process. Additionally, UV-vis spectroscopy, Mott-Schottky analysis, and UPS studies were used to determine the band edge locations of g-C3N4 and CoTiO3. In comparison to previously developed nanohybrids and their equivalents, the CTOCN-d photoanode follows the type II charge transfer mechanism, resulting in a higher photocurrent density of 55.51 mA cm-2.

Acceleration of bulk and surface charger transfer dynamics via FePi cocatalyst-coated Ti/(Sb)-Fe2O3:Sb/(Ti)-Fe2O3 type-II homojunction photoanode for photoelectrochemical performance

Hematite (α-Fe2O3) possesses notable benefits in the field of photoelectrochemical (PEC) water splitting. However, the overall low efficiency of the separation and transfer of photogenerated charge carriers significantly hinders its further utilization. Although the occurrence of an internal electric field has the potential to significantly augment the efficiency of charge separation and transfer, there is a crucial need to broaden the scope of its successful application. This study explores a strategy for modifying the coupling between homojunction formation with gradient doping and cocatalyst modification on hematite to boost PEC performance. The developed type II Ti-doped/(Sb-codoped) Fe2O3:Sb-doped/(Ti-codoped) Fe2O3 (Ti/(Sb)-HT:Sb/(Ti)-HT) homojunction with a staggered band alignment accelerated the bulk charge separation via an intrinsic built-in electric field, while the bulk conductivity was improved using a gradient co-doping approach. Furthermore, the deposition of a FePi cocatalyst expedited the transfer of holes from the photoanode to the electrolyte by increasing the surface states, thereby hastening the water oxidation kinetics. The resulting Ti/(Sb)-HT:Sb/(Ti)-HT@FePi photoanode exhibited a 78.7% increase in photocurrent density compared to the bare Ti-Fe2O3 photoanode (0.94–1.68 mA/cm2 at 1.23 VRHE), accompanied by a charge transfer efficiency of 72.5%. Comprehensive photoelectrochemical investigations revealed that the homojunction and cocatalyst play a vital role in improving the dynamics of both the bulk and surface of the hematite photoanode, thereby facilitating efficient water oxidation. These findings offer a deeper insight into the function of homojunction photoanodes adorned with cocatalysts in the solar water-splitting process.

CoMoP hole transfer layer functionally enhances efficiency and stability of BiVO4 based photoanode for solar water splitting

Engineering the hole transfer layer is a promising approach to suppress the bulk charge recombination of photoanodes for enhancing solar water splitting performance. Herein, functional cobalt-molybdenum bimetallic phosphide (CoMoP) layer are inserted between bismuth vanadate (BiVO4) and NiFeOx oxygen evolution cocatalyst (OEC) as hole transfer layer to construct an integrated photoanode (NiFeOx/CoMoP/BiVO4). This state-of-the-art NiFeOx/CoMoP/BiVO4 photoanode not only achieves a superior photocurrent density of 5.82 mA/cm2 at 1.23 V vs a reversible hydrogen electrode (vs RHE), but also an outstanding 60 h long-term photostability (100 mW/cm2). Such excellent PEC performance can be attributed to the engineering CoMoP hole layer in NiFeOx/BiVO4, promoting hole transfer, retarding bulk charge recombination and accelerating the surface water oxidation kinetics. This study contributes to the role of the hole transfer layer and sheds light on the development of effective and stable photoanodes for PEC water splitting.

Unravelling the effects of active site density and energetics on the water oxidation activity of iridium oxides

Understanding what controls the reaction rate on iridium-based catalysts is central to designing better electrocatalysts for the water oxidation reaction in proton exchange membrane electrolysers. Here we quantify the densities of redox-active centres and probe their binding strengths on amorphous IrOx and rutile IrO2 using operando time-resolved optical spectroscopy. We establish a quantitative experimental correlation between the intrinsic reaction rate and the active-state energetics. We find that adsorbed oxygen species, *O, formed at water oxidation potentials, exhibit repulsive adsorbate–adsorbate interactions. Increasing their coverage weakens their binding, thereby promoting O–O bond formation, which is the rate-determining step. These analyses suggest that although amorphous IrOx exhibits a higher geometric current density, the intrinsic reaction rates per active state on IrOx and IrO2 are comparable at given potentials. Finally, we present a modified volcano plot that elucidates how the intrinsic water oxidation kinetics can be increased by optimizing both the binding energy and the interaction strength between the catalytically active states.

Enhanced Water Oxidation of Hematite Photoanodes via Localized n‐p Homojunctions Induced by Gradient Zn2+ Doping

AbstractConstructing an internal electric field (IEF) within the hematite (Fe2O3) photoanode for highly efficient water oxidation performance with facilitated charge transfer and separation remains still a significant challenge. Unlike the conventional approach of creating interfacial electric fields through heterojunction design by introducing another semiconductor, a novel strategy is proposed for engineering localized n‐p homojunctions on the surface of Fe2O3 photoanode using gradient Zn2+ doping strategy. By implementing this approach, the inherent n‐type characteristics of Fe2O3 can be transformed into p‐type, thereby facilitating the formation of an n‐p junction with robust IEF, which enables more efficient charge separation and transfer. Additionally, the gradient Zn2+ doping is accompanied by the generation of oxygen vacancies, which further improves the charge transfer efficiency and accelerates water oxidation kinetics. As expected, the photocurrent density of optimized Fe2O3 photoanode at 1.23 V versus reversible hydrogen electrode is ≈2.6‐fold that of Fe2O3. This work provides a novel perspective on the design of localized n‐p homojunction within photoanodes for achieving high solar energy conversion efficiency.

In situ semi-etching of bimetallic LDH nanosheet arrays into FeNi-LDH/MOF to boost oxygen evolution reaction

The inherent sluggish kinetics of water oxidation is the core issue for electrochemical hydrogen production from water splitting. Metal organic frameworks (MOFs) with tunable porous structures, abundant coordination metal centers and large specific surface area are expected as efficient electrocatalysts. In this paper, FeNi-LDH/MOF composite nanostructures were successfully constructed on carbon cloth (CC) through partially converting iron-nickel layered double hydroxide (FeNi-LDH) into FeNi-MOF (NiFe(CN)5NO) by an in-situ semi-etching method. The MOF nanocrystals in this material are in-situ decorated on the surface of FeNi-LDH nanosheets, providing abundant open active sites and mass transfer channels for electrocatalysis. Thanks to the synergistic effect of the LDH and MOF, as well as the exceptional hierarchical architecture, the FeNi-LDH/MOF/CC as a self-supported electrode exhibits distinguished electrocatalytic OER performance, with a low overpotential of 263 mV@100 mA cm−2 and a small Tafel slope of 50.2 mV dec-1 in 1.0 M KOH. In addition, the catalyst exhibits good durability with almost constant current density during 24 h OER test. This work provides an effective way to design high-performance MOFs-based composite electrocatalytic materials.