Efficient Oxidation Catalysts Research Articles

Superior single-atom Pt/TiO2 mesoporous microspheres via microdrops-confined pyrolysis/deposition for low-temperature CO oxidation

This work demonstrate a polymer micelle-induced mesoporous single-atom Pt1/TiO2 microspheres with a mixed mother solution of triblock copolymer (Pluronic F127), H2PtCl6 and tetrabutyl titanate (TBT). The specific surface area and pore volume of mesoporous single-atom Pt1/TiO2 microspheres reach 179 m2/g and 0.39 cm3/g, respectively. The synthesis reaction is spatially confined in microdrops via aerosol spray. The obtained catalysts present superior activity for CO oxidation at low temperature. Typically, T100 (Temperature required to reach 100% conversion) of CO conversion (1.0% CO + 1.0% O2) is achieved at 120 °C with 0.5 at% Pt1/TiO2 catalysts, 50–60 °C lower than that with the same Pt loaded non-mesoporous catalysts from conventional photo-deposition and immersion-deposition of Pt on commercial TiO2 nanoparticles. Thus, this work paves a way to access efficient single-atom catalysts for CO oxidation.

Fabrication of tungstate metal foams as efficient catalysts for dimethyl sulfoxide oxidation in a microreactor

To overcome the problems of traditional catalyst in the microreaction technology, a microreactor system with tungstate metal foam catalyst was constructed and the catalytic efficiency were investigated by dimethyl sulfoxide (DMSO) oxidation reaction as a probe reaction. Three tungstate metal (CuWO4, NiWO4, FeWO4) foams were fabricated, and inherited the porous structure from the metal foam and had a high loading density of tungstate metal crystal particles. In the lab-built flat-plate microreactor, the effects of reaction temperature, residence time, molar ratio and pH on the yield of dimethyl sulfone (MSM) were investigated, and the tungstate metal foams showed prefect catalytic activity. Compared with NiWO4 foam and FeWO4 foam, the larger specific surface area and higher porosity endow CuWO4 with a better catalytic performance. When the reaction temperature was 80 °C, the residence time was 40 min, the molar ratio was 1:1 and the pH value of the reaction system was 3, the yield of MSM reached 82.1%. Furthermore, the NiWO4 foam catalyst system showed a better performance compared with other two catalyst system. This work indicates the potential opportunity of the construction of various metal foam catalysts in the versatile continuous microreaction technology.

Atomic-level mechanism and microkinetics of HCHO oxidation over K-doped MnO2 catalysts

K-doped MnO2 is regarded as an efficient catalyst for HCHO oxidation. A combined study of density functional theory (DFT) and microkinetic modeling was implemented to investigate the role of potassium doping in the catalytic reactivity of MnO2 towards HCHO oxidation. The DFT-derived thermodynamic stability analysis indicates that the K-doped MnO2 surface is more stable than the pristine MnO2 surface under the practical experimental conditions. The introduction of K ion is energetically beneficial to the adsorption of HCHO and O2 by charge transfer from potassium to the catalyst surface. The HCHO oxidation paths show that the rate-determining step is the second dehydrogenation reaction. The best catalytic activity of MnO2@K-1 is associated with the abundant Mn atom with a high chemical valence on the catalyst surface. Specially, K doping has little effect on the adsorption of water, but promotes the production of OH group by reducing the energy barrier of hydrolysis. The hydroxylated surface is favorable for the two-step cleavage of the C-H bond. The overall reaction rate of HCHO oxidation on the K-doped MnO2 catalyst is much higher than that on the pristine MnO2. At low temperatures, the reaction rate is relatively insensitive to the pressure change, while the oxidation rate gradually rises with the increasing of pressure at high temperatures. K doping is conducive to boosting the reaction rate of HCHO oxidation, which is associated with the stronger interaction of reactants with K-doped catalysts.

Pore-engineering-dependence and hydrophobicity-dependence on stannosilicate zeolite catalyst for efficient Baeyer-Villiger oxidation

As robust heterogeneous catalysts, stannosilicate zeolites (in particular Sn-Beta) exhibit excellent catalytic performance in aqueous Baeyer-Villiger oxidation due to their unique activation ability of carbonyl group. For a specific Sn-containing zeolite, pore-engineering and hydrophobicity are generally two coupled factors to impact catalytic behavior. How to distinguish the function of each factor in this selective oxidation is still a pending question. Bearing this in mind, five stannosilicate zeolites (Sn-MFI, Sn-MWW, Sn-Beta, Sn-MCM-41, and Sn-Y) were prepared to establish the relationship between the structure (Lewis acidity, pore-engineering, and hydrophobicity) and catalytic performance. Particularly, hierarchical Sn-Y zeolite was post-synthesized by a simple solid-state ion-exchange method, where Sn4+ ions were incorporated into zeolite framework via reacting with silanol nests derived from dealumination process. In comparison with other stannosilicate zeolites, the obtained Sn-Y possessed excellent catalytic activity in Baeyer-Villiger oxidation irrespective of using aqueous hydrogen peroxide or bulky tert-butyl hydroperoxide as the oxidant. Structure-performance relationship revealed that Lewis acid site was the catalytically active center and the catalytic activity was depended on zeolite pore-engineering and hydrophobicity in aqueous B-V oxidation system. The relatively high catalytic activity of Sn-Y zeolite was ascribed to its excellent hydrophobicity and opened channel system. The former can be further enhanced by silanization treatment. Finally, the recyclability and deactivation mechanism were given insight. This work is aimed to provide some guidance for elaborately designing efficient stannosilicate zeolite catalyst for Baeyer-Villiger oxidation by precisely modulating pore-engineering and hydrophobicity.

Highly Efficient RGO-Supported Pd Catalyst for Low Temperature Hydrocarbon Oxidation

The work presents Pd-containing catalysts for practical application with enhanced low-temperature activity in the complete oxidation of volatile organic compounds (VOCs) using innovative combinations of reduced graphene oxide (RGO) and alumina. The catalysts were characterized by XRD, SEM, TEM, XPS, low-temperature N2-adsorption, and CO chemisorption. The tests on complete catalytic oxidation of different VOC (propane, butane, hexane, dimethyl ether, toluene, propylene) and CO were carried out. The reaction kinetics and the mechanism of the reaction of complete oxidation of toluene are being investigated in detail. The results show that the new catalyst design makes it able to completely oxidize the studied VOCs and CO at low temperatures (100–350 °C) with long-term stability. Using a variety of instrumental methods, it was established that for high activity and long-term stability, the optimal ratio Pd/PdO should be close to 1:1. The most probable mechanism of complete toluene oxidation is the mechanism of Langmuir–Hinshelwood. The high activity and the weak effect of water on the catalyst performance leads to further perspectives for the application of the currently developed approach for the preparation of large-scale monolithic catalytic systems for air pollution control.

Effects of carbon vacancies on the CO oxidation on Cu double atom catalyst supported by graphene

The activity of double metal atoms is closely related to their chemical coordination environments. In this work, CO oxidation on Cu double atom catalyst loaded on defective graphene with triple carbon vacancy (Cu2-TG) and quadruple carbon vacancy (Cu2-QG) has been comprehensively studied through DFT calculations. Empty Cu-3d orbital is created through charge transfer from Cu atom to carbon atom of graphene, which is parallel to the basal plane of graphene for one Cu atom and nearly perpendicular to the basal plane for the other Cu atom in Cu2-TG. While the empty Cu-3d orbital is parallel to the basal plane for both Cu atoms in Cu2-QG. The delocalized orientation of empty Cu-3d orbital in Cu2-TG makes it more convenient to accept electrons and more active. This is verified through the larger adsorption energies of -1.74 eV and -1.68 eV for O2 and CO molecules on Cu2-TG, as well as the smaller values of -0.20 eV and -0.40 eV on Cu2-QG, respectively. Because of the weak interactions between Cu2-QG and gas molecules, only Cu2-TG is further considered to catalyze the CO oxidation. The maximum barrier of CO oxidation along ER path is 1.75 eV on Cu2-TG, while that is only 0.39 eV along LH path, which indicates a smooth reaction progress on Cu2-TG. The electronic structures show that the Cu atom can accept electrons through its empty 3d orbital and lose electrons through its filled 3d orbital with an “acceptance and feedback” mechanism. Cu2-TG can move the 5σCO orbital downshift significantly, which causes the 5σCO/1πCO orbitals very close to 5σO2/1πO2 orbitals and facilitates the formation of OC-OO bond along LH path. These results indicate that the synergistic effects between the two Cu atoms and the triple carbon vacancy make Cu2-TG to be an efficient CO oxidation catalyst.

Fe-doped MnO2 as an efficient catalyst for low temperature propane oxidation

Manganese oxides were received extensive attention on account of its low cost, variable valence state and excellent redox properties. Herein, we successfully prepared various Fe-doped MnO2 catalysts to further improve the catalytic activity of MnO2 on propane. Physicochemical characterization results displayed that with the increase of Fe doping amounts, the crystalline phase of MnO2 gradually changed from α-MnO2 and β-MnO2 to Fe2O3, the particle size of catalysts decreased and the specific surface area increased. However, increasing the content of Fe could not monotonically enhance the catalytic performance of catalysts on propane. When the molar ratio of Fe/Mn was 0.25, the largest amount of Mn4+ species and lattice oxygen species were exposed on the surface of Mn8Fe2, and showed the best low temperature reducibility, which was ascribed to the synergistic effect between Mn and Fe was enhanced. It presented optimal catalytic activity for propane oxidation with temperature of propane conversion at 90% (T90) as low as 279 °C under 0.1% propane and 5% O2. This work provided a new way to design and synthesize efficient non-noble metal catalysts for the elimination of propane, which had certain application value.

Nb2S2C Monolayers with Transition Metal Atoms Embedded at the S Vacancy Are Promising Single-Atom Catalysts for CO Oxidation.

Single atoms anchored on stable and robust two-dimensional (2D) materials are attractive catalysts for carbon monoxide (CO) oxidation. Here, 3d (Fe-Zn), 4d (Ru-Cd), and 5d (Os-Hg) transition metal-decorated Nb2S2C monolayers were systematically studied as potential single-atom catalysts for low-temperature CO oxidation reactions by performing first-principles calculations. Sulfur vacancies are essential for stabilizing the transition metals anchored on the surface of defective Nb2S2C. After estimating the structure stability, the aggregation trend of the embedded metal atoms, and adsorption strength of reactants and products, Zn-decorated defective Nb2S2C is predicted to be a promising catalyst to facilitate CO oxidation through the Langmuir-Hinshelwood (LH) mechanism with an energy barrier of only 0.25 eV. Our investigation indicates that defective carbosulfides can be promising substrates to generate efficient and low-cost single-atom catalysts for low-temperature CO oxidation.

In situ Raman study of high potential scan enhanced Pt/C and Pd/C catalyst performance for ethanol oxidation

The efficient catalysis of ethanol oxidation (EOR) is of paramount importance for the progress of energy conversion and storage technologies. We investigate the improved catalytic performance of commercial J-M Pt/C and Pd/C catalysts for ethanol oxidation by utilizing high potential scanning. By employing in situ Raman spectroscopy, we analyze the reaction intermediates during electrochemical reactions. Our findings highlight that the Pd/C catalyst exhibits remarkable enhancements in catalytic activity and stability, which can be attributed to the activation at high potentials on Pd/C electrode. Interestingly, different results are observed between Pt/C and Pd/C catalysts under the same experimental conditions. This study provides valuable insights into the design and development of efficient catalysts for ethanol oxidation.

Bifunctional bimetallic oxide nanowires for high-efficiency electrosynthesis of 2,5-furandicarboxylic acid and ammonia

It is an appealing avenue for electrosyntheis of high-valued chemicals at both anode and cathode by coupling 5-hydroxymethylfurfural (HMF) oxidation and nitrate reduction reactions simultaneously, while the development such bifunctional electrocatalysts is still in its infancy with dissatisfied selectivity and low yield rate. Here, we first report that Zn-doped Co3O4 nanowires array can be served as an efficient and robust dual-functional catalyst for HMF oxidation and nitrate reduction at ambient conditions. Specifically, the catalyst shows a faradaic efficiency of 91 % and a yield rate of 241.2 μmol h−1 cm−2 for 2,5-furandicarboxylic acid formation together with a high conversion of nearly 100 % at a potential of 1.40 V. It also displays good cycling stability. Besides, the catalyst is capable of catalyzing the reduction of nitrate to NH3, giving a maximal faradaic efficiency of 92 % and a peak NH3 yield rate of 4.65 mg h−1 cm−2 at a potential of –0.70 V. These results surpass those obtained using pristine Co3O4 and are comparable to those of state-of-the-art electrocatalysts. Moreover, the catalyst is further employed as the cathode catalyst to assemble a Zn–nitrate battery, giving a peak power density of 5.24 mW cm−2 and a high yield rate of 0.72 mg h−1 cm−2. Theoretical simulations further reveal that Zn-doping favors the adsorption and dissociation of nitrate and HMF species and reduces the energy barrier as well. Our work demonstrates the potential interest of Co3O4-based materials for the highly selective production of valuable feedstocks via ambient electrolysis.

Enhanced Catalytic Aryl Alkene Oxidation by Constructing Hierarchical Polyoxometalate‐Based Metal‐Organic Framework

AbstractAchieving highly selective oxidation of aryl alkenes to aldehydes is of great significance in chemical industry. Herein, the performance of catalytic aryl alkene oxidation is enhanced via constructing a hierarchical fractal polyoxometalate‐based metal–organic framework (POM@MOF) containing hierarchical pores and layered surface structure, which improve the mass transfer efficiency of substrates and increase the accessibility to active POMs clusters. Accordingly, the activity of fractal POM@MOF is increased by 4.8 times compared with microporous counterpart in 4‐tert‐butylstyrene oxidation to aldehyde product. This work paves a way for designing efficient catalysts for selective oxidation of aryl alkenes via increasing the accessibility of active sites and broadening the diffusion channels by hierarchical construction.

Polyhedral Coordination Determined Co‐O Activity for Electrochemical Oxidation of Biomass Alcohols

AbstractEarth‐abundant transition metal oxides are promising electrocatalysts for oxidation of biomass alcohols. Here, CoO and Co3O4 are selected as representative cobalt oxide catalysts and grown on carbon fiber paper (CFP) electrodes to reveal the interplay between electronic structure and catalytic activity of catalysts for oxidation of glycerol, diols, and monohydric alcohols. In situ electrochemical tests elucidate that the CoO/CFP electrode has lower interfacial impedance, higher charge transfer, faster oxidation rate, and thereby the higher catalytic activity for alcohol oxidation than the Co3O4/CFP electrode. Especially for glycerol oxidation, the CoO/CFP electrode only requires 1.32 V to reach 10 mA cm−2, the potential is 120 mV lower than that for the Co3O4/CFP electrode. The CoO/CFP electrode can also produce value‐added products such as formate, acetate, and glycolate with high selectivity and efficiency at low energy consumptions from oxidation of biomass alcohols. Theoretical calculations further confirm the dominant role of octahedrally coordinated Co‐O sites in adsorption, activation, and oxidation of C3‐C1 alcohols. This work sheds light on the design of highly efficient transition metal oxide catalysts for oxidation of alcohols by populating octahedral sites in the crystal structure.

Polyoxometalate‐Incorporated CuI‐Resorcin[4]arene Metal‐Organic Complexes as Heterogeneous Catalysts for Catalytic Oxidation of Mustard Gas Simulant

AbstractExploring efficient heterogeneous catalysts for catalytic oxidation of chemical warfare agents (CWAs) is highly desired. As a class of discrete anionic metal oxide clusters, polyoxometalates (POMs) provide abundant catalytic active sites, thus resulting their rich redox properties. Here, a family of known POM‐incorporated CuI‐resorcin[4]arene metal‐organic complexes, namely, [Cu4(TPTR4A)2][PW12O40](OH) ⋅ 0.5DMA ⋅ 5H2O (Cu‐PW), [Cu4(TPTR4 A)2][PMo12O40](OH) ⋅ 2DMA ⋅ H2O (Cu‐PMo) and [Cu4(TPTR4A)2][SiW12O40] ⋅ 2.5DMA (Cu‐SiW) were utilized as catalysts to promote the oxidation of 2‐chloroethyl ethyl sulfide (CEES). Strikingly, compared to the novel compound [Cu3Cl6(TPTR4A)(DMA)] ⋅ CH3CH2OH (defined as Cu‐T), the three complexes exhibited excellent stability, indicating that the integration of POMs and metal–organic units could improve the stability of the compounds. Moreover, Cu‐PMo and Cu‐PW showed higher activities for the catalytic oxidation of CEES to CEESO with selectivities both of 99 %.

A unique sandwich-structured Ru-TiO/TiO2@NC as an efficient bi-functional catalyst for hydrogen oxidation and hydrogen evolution reactions

Developing active and stable non-Pt electrocatalysts for hydrogen oxidation (HOR) and evolution reactions (HER) are critical for anion exchange membrane fuel cells and water electrolyzers. Herein, we report a highly active and robust electrocatalyst Ru-TiO/TiO2@NC, in which Ru nanoclusters are sandwiched between TiO/TiO2 nanosheets and nitrogen-doped carbon layers. Taking advantage of both the optimized Ru-TiO/TiO2 interaction and the conductive carbon coating layers, the Ru-TiO/TiO2@NC exhibits both exceptional HOR/HER activity and superior stability, outperforming Pt/C in the alkaline solution. The HOR mass activity reaches up to 107.2 A gRu-1 at an overpotential of 50 mV, and the specific exchange current density is 0.271 mA cm−2. The HER overpotential at 10 mA cm−2 is only 39 mV, 34 mV lower than required by Pt/C. More importantly, the Ru-based catalyst exhibits excellent anti-oxidation ability by virtue of the unique sandwich structure. Density functional theory calculations discover that the d-band center of Ru in Ru-TiO/TiO2 is downshifted by 0.29 eV compared to Ru-TiO2, decoupling and optimizing the Had/OHad adsorption on Ru, i.e., Had is promoted, while OHad is inhibited and transferred to TiO/TiO2. As a result, (i) the energy required by the potential determining step of HOR/HER is lowered, and (ii) the anti-oxidation ability of the Ru-TiO/TiO2 is enhanced. This work not only addresses the issue of Ru passivation at high anode potentials but also provides an innovative and versatile approach to designing advanced electrocatalysts.

Waste to wealth: H2S-free fabrication of Fe-ZnS/NC by industrial lignin self S-doping for efficient lignin aerobic oxidation

Industrial lignin mostly contains sulfur, which poisons metal catalysts easily. Metal sulfides with good S-resistance could be used as efficient catalysts for lignin oxidation, while metal sulfides preparation involved corrosive H2S. Here in, we proposed H2S-free fabrication of bimetallic Fe-ZnS/NC by industrial lignin self S-doping. The Fe-ZnS/NC 650 exhibited efficient oxidation activity (> 99% conversion) for β-O-4 cleavage and good S-resistance for industrial lignin oxidation. Density functional theory revealed the synergistic effect of FeS and ZnS in lignin oxidation, where FeS tended to activate O2 into superoxide radical (O2-•) and ZnS contributed to the polarization of β-O-4. The dual sites greatly reduced the migration distance of O2-• to the polarized β-O-4, facilitating the C-O/C-C cleavage. Hence, Fe-ZnS/NC 650 selectively converted lignin into carbonyl-containing aromatics with up to 92% selectivity under alkaline-free condition. This work developed a novel strategy using lignin-derived metal sulfide without external sulfur source for efficient lignin degradation.

Fabrication of highly dispersed Pd-Mn3O4 catalyst for efficient catalytic propane total oxidation

Adjusting the interaction between dual active components for enhancing volatile organic compounds (VOCs) degradation is an effective but still challenging means of air pollution control. Herein, a limited pyrolysis oxidation strategy was adopted to prepare Pd-Mn3O4 spinel catalysts with uniform morphology and active component dispersion. Among these, 1.08Pd-Mn3O4 presented the highest catalytic efficiency with a T90 value of 240 °C, which was 94 °C lower than that of Mn3O4. Characterization and density functional theory (DFT) calculation results revealed that the strong metal-support interaction (SMSI) effect between Pd and Mn3O4 promoted the redistribution of surface charges, thus strengthening the oxidation-reduction ability of the active sites. Moreover, the SMSI effect led to a better migration of surface oxygen species, and boosted the generation of active surface oxygen species. Simultaneously, the Pd catalyst further reduced the energy barrier in the initial stage of the dehydrogenation of propane. Overall, this study provided a novel design strategy for dual active components catalysts with SMSI effect and extended the application of these catalysts in the important field of VOCs elimination.

A highly efficient bifunctional copper catalyst for Baeyer-Villiger oxidation of cyclohexanone: Two different active centers and the reaction path investigation

Polycaprolactone is a significant alternative to nondegradable plastic, and the synthesis of its monomer ε-caprolactone (ε-CL) has obtained increasing attention. Here, one kind of Cu-SiO2 bifunctional catalyst with highly dispersed copper species and various metal valences was developed and applied in Baeyer − Villiger (B-V) oxidation for cyclohexanone (Cy=O) to produce ε-CL with O2/benzaldehyde. The Lewis acidity and the different valence of the copper species could be adjusted by two simple post-treatment methods. The optimal Cu-SiO2-60-1.5 exhibits > 99 % conversion of Cy=O and > 99 % selectivity to ε-CL with high efficiency of BEA. The enhancement primarily originates from the synergism of Cu2+, Cu+, and the Lewis acidity of the catalysts. In addition, the possible mechanisms and realistic reaction path were proposed and verified by combing the characterization and DFT calculations. It clarifies the not well-understood reaction mechanism in B-V oxidation of Cy=O. And it reveals that the formation of the Ph-CO3H intermediate is rate-limiting step, and it is beneficial for the vital “Criegee” intermediates formation thanks to its lower activation energy. This work provides a promising strategy for designing suitable oxidative catalysts and clarifies realistic reaction path of B-V oxidation of Cy=O, which could improve the development of degradable plastics.

Computational Study of Single Metal Atom Anchored on Black Phosphorus for Methane Oxidation to Methanol by Nitrous Oxide.

Direct conversion of methane to high-value-added transportable methanol is a great challenge, which requires high energy input to break the strong C-H bond. Developing efficient catalysts for methane oxidation to methanol under mild conditions is of vital importance. In this work, single transition metal atoms (TM=Fe, Co, Ni, Cu) anchored on black phosphorus (TM@BP) were studied as catalysts to assist the methane oxidation to methanol by means of first-principles calculations. The results indicate that Cu@BP exhibits an outstanding catalytic activity through the radical reaction pathways and the formation of the Cu-O active site is rate-determining with an energy barrier of 0.48 eV. Meanwhile, electronic structure calculations and dynamic simulations show that Cu@BP offers excellent thermal stability. Our calculations provide a new approach for the rational design of single atom catalysts for methane oxidation to methanol.

Synthesis of highly efficient Cu-PtRu ternary metal catalyst for methanol oxidation

Development of remarkably catalytic activity and CO resistance catalyst has become a focus for methanol oxidation. In this study, the irregular polyhedral of Cu was synthesized by simple electrochemical deposition method. Then Pt-Ru alloy nanoclusters were uniformly deposition on Cu polyhedra to prepare Cu-PtRu ternary alloy materials. The morphology and structure of the ternary alloy were studied by scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM). Electrochemical results showed that Cu-PtRu exhibited favorable catalytic capacity and high CO resistance for methanol oxidation. In various proportion of Pt-Ru, Cu-Pt5.2Ru1 showed the highest electrocatalytic activity (638.2 mA mgPt−1) for methanol oxidation, which was 2.2 and 2.84 folds relative to commercial Pt/C (Pt wt.20%) and PtRu/C (Pt wt.30%), respectively. Therefore, Cu-Pt5.2Ru1 might be used as a novel structure electro-catalyst for methanol oxidation.

The synthesis of Cr and P codoped NiMoO4 nanospheres as efficient catalyst for urea oxidation and oxygen evolution reaction

The design of reasonable and efficient electrocatalysts is imperative in large scale water splitting applications. In this paper, NiMoO4 nanospheres doped with Cr and P were constructed by hydrothermal method and phosphating process as electrocatalysts for water splitting, and the doping of Cr and P effectively modulated the electronic structure, which led to an increase in the active sites and an increase in the intrinsic activity of each site. Notably, Cr/P–NiMoO4@NF presented excellent urea oxidation reaction (UOR) performance (1.312V @ 10 mA cm−2) and oxygen evolution reaction (OER) performance (overpotential 309 mV @ 10 mA cm−2) in electrolytes of 1 M KOH and 1 M KOH with 0.5 M urea because of the doping effect of Cr and P. The experimental analysis showed that the improvement of electrochemical performance was mainly reflected in the accelerated electron transfer rate, increased exposure of reaction sites and improved metal properties and so on. For Cr/P–NiMoO4@NF, after a long time UOR and OER stability test, some changes have taken place in the appearance of the sample, which increases the contact area and provides more active sites, making the catalytic performance of the sample have no too obvious attenuation. Density functional theory calculation shows that the Cr/P–NiMoO4 material exhibits higher urea adsorption energy, indicating that urea is preferentially adsorbed on its surface. The Cr/P–NiMoO4 material shows more state density near the Fermi level, indicating that the introduction of Cr and P enhances the conductivity of the Cr/P–NiMoO4 material. This work provides a novel idea for the research and exploitation of low cost and robust UOR and OER electrocatalysts.