Catalyst For Hydrolysis Research Articles

Tuning catalytic performance of platinum single atoms by choosing the shape of cerium dioxide supports.

The local coordination environment of single atom catalysts (SACs) often determines their catalytic performance. To understand these metal-support interactions, we prepared Pt SACs on cerium dioxide (CeO2) cubes, octahedra and rods, with well-structured exposed crystal facets. The CeO2 crystals were characterized by SEM, TEM, pXRD, and N2 sorption, confirming the shape-selective synthesis, identical bulk structure, and variations in specific surface area, respectively. EPR, XPS, TEM and XANES measurements showed differences in the oxygen vacancy density following the trend rods > octahedra > cubes. AC-HAADF-STEM, XPS and CO-DRIFTS measurements confirmed the presence of only single Pt2+ sites, with different surface platinum surface concentrations. We then compared the performance of the three catalysts in ammonia borane hydrolysis. Precise monitoring of reaction kinetics between 30-80 °C gave Arrhenius plots with hundreds of data points. All plots showed a clear inflection point, the temperature of which (rods > octahedra > cubes) correlates to the energy barrier of ammonia borane diffusion to the Pt sites. These activity differences reflect variations in the - facet dependent - degree of stabilization of intermediates by surface oxygen lone pairs and surface-metal binding strength. Our results show how choosing the right macroscopic support shape can give control over single atom catalysed reactions on the microscopic scale.

Acid catalyst screening for hydrolysis of post-consumer PET waste and exploration of acidolysis

We screen various acid catalysts (mineral, carboxylic, carbonic acids, zeolites, ionic liquids, and metal salts) for PET hydrolysis.

The mechanism and challenges of cobalt-boron-based catalysts in the hydrolysis of sodium borohydride

Among boron compounds, NaBH4 has emerged as a prominent candidate for hydrogen energy sources owing to its environmentally friendly characteristics and a high hydrogen content of up to 10.6 wt%.

Catalytic hydrolysis of methyl mercaptan and methyl thioether on hydroxyl-modified ZrO2: a density functional theory study.

The purification and removal of organic sulfur from natural gas is conducive to increasing the added value of natural gas and reducing environmental pollution. In this study, the adsorption properties of methyl mercaptan (CH3SH), dimethyl sulfide (C2H6S) and H2O on the surface of hydroxyl-modified ZrO2 were investigated using density functional theory (DFT) calculations. Additionally, a reaction mechanism was proposed for hydroxyl-modified ZrO2 catalyzing the hydrolysis of CH3SH and C2H6S. The chemisorption of H2O molecules on the catalyst surface is attributed to H-O and H-Zr bonds. The chemisorption of CH3SH and C2H6S on the catalyst surface is attributed to Zr-S bonds. Competitive adsorption between the three gases exists only between CH3SH and C2H6S. It reveals the water-resistant properties of hydroxyl-modified ZrO2 in desulfurization. The adsorption energies of the three gas molecules on the hydroxyl-modified ZrO2 surface are in the order of CH3SH - (Zr) > C2H6S - (Zr) > H2O - (OH). The natural hydrolysis of CH3SH and C2H6S is a heat-absorbing process that cannot occur spontaneously. The rate-determining step for CH3SH catalytic hydrolysis is the formation of CH3O. The fracture of CH3SHO is the rate-determining step for C2H6S catalytic hydrolysis. The depletion of the surface hydroxyl groups can be replenished by the dissociation of H2O molecules. Hydroxyl-modified ZrO2 facilitated the hydrolysis process of CH3SH to a greater extent than that of C2H6S. This study provides theoretical guidance for industrial applications and the design of hydroxyl-containing hydrolysis catalysts.

Waugh Type Polyoxometalate Enneamolybdomangate(IV) as an Acid Catalyst for Hydrolysis and as an Oxidant for Aspirin: A Kinetic Study

The oxidations of aspirin and salicylic acid by enneamolybdomanganate(IV) were studied in perchloric acid medium. The aspirin undergo hydrolysis prior to the oxidation to generate salicylic acid, which was found to be catalyzed by both HClO4 as well as the oxidant. The rate of hydrolysis of aspirin catalyzed by the oxidant was found to be lesser than that of HClO4. A mechanism based on the kinetic results is proposed for oxidation of both aspirin and salicylic acid. Initially, aspirin undergo hydrolysis to give salicylic acid, which is catalyzed by both the oxidant, which also acts as an acid catalyst and the HClO4 used. The salicylic acid generated in prior hydrolysis reacts with an oxidant undergoing oxidative decarboxylation by enneamolybdomanganate(IV) in a rate determining step generating phenol. Further oxidation of phenol by another oxidant molecule gives the final product p-benzoquinone in a fast step. The mechanism of oxidation of salicylic acid was also studied under identical conditions as that of aspirin and found to be similar except its prior hydrolysis. A plausible mechanism was proposed and the rate laws for both the substrates were derived. In order to understand the intervention of free radicals the reaction was studied in presence of added acrylonitrile. The formation of copious precipitate due to polymerization of added acrylonitrile was not observed and the values of kobs also remain constant in presence of added acrylonitrile. The formation of MnIII was also studied in presence of added tetrasodium pyrophosphate, which did not affect the values of kobs. Therefore, the formation of free radical and MnIII was excluded while proposing mechanisms for both the substrates. The effect of added products Mn2+ and molybdate also did not have any effects indicating no prior equilibria involving these two products. The effect of ionic strength and solvent polarity are in favour of the reaction between two neutral molecules. The activation parameters were determined and support an outer sphere reaction with formation of a weak precursor complex between the reactants was proposed for both aspirin and salicylic acid.

Catalyst for lactose hydrolysis based on zeolite Y modified with Fe species by ultrasound treatment

Research has focused on biomass as a sustainable energy source, driving biomass valorization to convert carbohydrates. The price of lactose has dropped below the production cost, urging exploration for diverse applications, such as conversion into value-added compounds. Zeolites, especially Y zeolite, enhance hexose conversion when modified with metals. Fe-modified zeolites show promise, with controlled Si/Al ratios impacting acidity and selectivity. The recent challenges remain in active site comprehension, catalyst tunability, and reaction optimization. Therefore, this study explores the selective hydrolysis of lactose, limiting undesired side-product formation catalyzed through a sono-assisted modified zeolite Y with Fe. The obtained series of Fe-modified zeolite Y were evaluated for the hydrolysis of lactose in a screening experiment. The samples with the higher potential were further used to optimize reaction conditions by a response surface methodology (RSM). This revealed that the samples prepared at high pH generated more impurities and that higher temperatures and lactose concentrations favored hydrolysis. Despite their apparent similarities, the selected Fe-modified zeolite Y samples (Fe5Y and FeYII) highlight distinct catalytic behaviors and active sites. Employing UV-Vis spectroscopy, FTIR spectroscopy, and magnetic thermal gravimetric analysis (MTGA), various Fe active sites were detected, including α-Fe(II), FeOx nanoparticles, and iron oxides. These active sites give insight into the mechanisms involved with temperature and time, which play critical roles—evidencing the potential of sono-assisted iron modification of zeolite Y to achieve selective lactose hydrolysis. These findings contribute to understanding metal-zeolite composites as bifunctional catalysts and their application in sustainable processes. Furthermore, this research highlights the complexity of catalytic reactions of modified zeolites and their potential for fine-tuning active sites for various applications, particularly lactose hydrolysis. Such advancements hold the promise of propelling the field of sustainable energy and catalysis towards a more efficient and environmentally friendly future.

A robust mesoporous sulfated zirconium‐doped KIT‐6 solid acid catalyst for the hydrolysis of microcrystalline cellulose

AbstractBACKGROUNDThe exploration of a robust solid acid catalyst for the efficient hydrolysis of cellulose is a research hotspot due to the need for clean production and sustainable development. KIT‐6 silica offers abundant three‐dimensionally interconnected mesopores, which are expected to be superior to mesoporous structures with one‐ or two‐dimensional channels due to faster diffusion of reactants and products during reaction. The catalytic conversion of microcrystalline cellulose is examined in detail over a functionalized KIT‐6 catalyst prepared by the method of Zr addition and subsequent sulfation.RESULTSIn terms of cellulose conversion and product yield, the activity of the catalysts followed the order of sulfated Zr‐KIT‐6 > Zr‐KIT‐6 > SO42−‐KIT‐6 > KIT‐6. Over the sulfated Zr‐KIT‐6 catalyst with a Si/Zr molar ratio of 7:1, a maximum cellulose conversion of 95.0% was achieved with glucose yield of 23.4%, 5‐hydroxymethylfufural yield of 4.9% and levulinic acid yield of 11.7% under the optimized reaction conditions: reaction temperature of 200 °C, reaction time of 2 h, catalyst amount of 0.3 g, cellulose‐to‐water mass ratio of 1:1.CONCLUSIONThe sulfated Zr‐KIT‐6 catalyst possessed the strongest and richest Brønsted acid sites, which readily provided protons for the cleavage of β‐1,4 glycosidic bonds in cellulose, thus conferring superior catalytic activity in cellulose hydrolysis. A plausible pathway at the initial stage of cellulose hydrolysis over the catalyst was proposed. © 2023 Society of Chemical Industry (SCI).

Optimizing Co2+ concentration on high-index Co3O4 facets enhances the catalytic performance in NaBH4 hydrolysis

Hydrogen is a viable alternative to fossil fuels due to its clean-burning properties and high energy density. However, a key challenge lies in the environmentally friendly production and storage of H2. NaBH4 could provide a solution by efficiently storing and releasing H2 through hydrolysis. Current catalysts for NaBH4 hydrolysis often contain cobalt (Co) and precious metals, raising concerns about their environmental impact and cost. To address this, this work proposes the development of efficient Co-only catalysts. Specifically, we explore the role of different crystal facets, specifically (311) and (220), in Co3O4 nanoparticles, demonstrating that an elevated CoO concentration in the (220) facet results in better catalysis for NaBH4 hydrolysis compared to traditional Co/precious metal composites. This improved catalyst shows promise for sustained use and minimal loss of catalytic activity, making it a potential solution for clean H2 production. Additionally, the findings may have broader applications in electrocatalysis and photocatalysis.

Hydrolysis of polyethylene terephthalate by ZSM-5 combined with supercritical carbon dioxide under neutral environment

Polyethylene terephthalate (PET) is a kind of stable polyester, which is difficult to be degraded in the natural environment, and the waste PET causes severe environmental problems. To achieve efficient and environmentally friendly hydrolysis of PET, we employed ZSM-5 as a catalyst for neutral hydrolysis of PET in the presence of supercritical carbon dioxide (SCCO2). This study demonstrates that the existence of SCCO2 in the system enhances PET hydrolysis efficiency. The swelling effect of SCCO2 on PET can relax the PET segment and promote the mass transfer of water molecules in the PET bulk phase. However, excessive pressure of SCCO2 leads to plasticization of PET which increases the crystallinity of PET and hinders hydrolysis. The activation energy was measured under different pressures, revealing a decrease in activation energy with increasing pressure below 7.5 MPa. When the pressure exceeds 7.5 MPa, the activation energy increases due to plasticization. Through the density functional theory (DFT) analysis combined with the experimental results, it has been confirmed that Brønsted acid on ZSM-5 plays a more important role than Lewis acid in the system.

Dandelion-like ZIF-67 supported ternary transition metal borides as efficient hydrolysis catalysts for KBH4

The development of high-efficient and low-cost catalysts is crucial for promoting KBH4 hydrolysis to produce hydrogen. Herein, ZIF-67 supported cobalt-molybdenum-nickel based boride (Co–Mo–Ni–B/ZIF-67) nanocomposites with dandelion-like morphology were designed as catalysts of KBH4 hydrolysis reaction and were synthesized via the chemical reduction process. Moreover, the element ratio and the loading amount of Co–Mo–Ni–B were optimized, and effects of KBH4 concentration, KOH concentration, and reaction temperature on catalytic performances were studied. As expected, ZIF-67 substrate avoids the agglomeration of amorphous Co–Mo–Ni–B, and the synergy between ZIF-67 and uniformly dispersed Co–Mo–Ni–B active substances accelerates hydrogen generation rate. As a result, the maximum hydrogen generation rate of 17400 mL min−1 g−1 is achieved with the optimized KOH concentration of 10% and KBH4 concentration of 6% at the reaction temperature of 30 °C. In addition, Co–Mo–Ni–B/ZIF-67 exhibits moderate durability performance with a cyclic retention rate of 51.9 % after five cycles. This dandelion-like structure design provides an idea for the development of efficient catalyst for hydrolysis of borohydrides.

COF-supported zirconium oxyhydroxide as a versatile heterogeneous catalyst for Knoevenagel condensation and nerve agent hydrolysis

A composite of catalytic Lewis acidic zirconium oxyhydroxides (8 wt%) and a covalent organic framework (COF) was synthesized. X-ray diffraction and infrared (IR) spectroscopy reveal that COF's structure is preserved after loading with zirconium oxyhydroxides. Electron microscopy confirms a homogeneous distribution of nano- to sub-micron-sized zirconium clusters in the COF. 3D X-ray tomography captures the micron-sized channels connecting the well-dispersed zirconium clusters on the COF. The crystalline ZrOx(OH)y@COF's nanostructure was model-optimized via simulated annealing methods. Using 0.8 mol% of the catalyst yielded a turnover number of 100-120 and a turnover frequency of 160-360 h-1 for Knoevenagel condensation in aqueous medium. Additionally, 2.2 mol% of catalyst catalyzes the hydrolysis of dimethyl nitrophenyl phosphate, a simulant of nerve agent Soman, with a conversion rate of 37% in 180min. The hydrolytic detoxification of the live agent Soman is also achieved. Our study unveils COF-stabilized ZrOx(OH)y as a new class of zirconium-based Lewis+ Bronsted-acid catalysts.

Air-Stable 14-Electron Rhodium(III) Complexes Bearing Si,N Ligands as Catalysts in Hydrolysis of Silanes

Air-Stable 14-Electron Rhodium(III) Complexes Bearing Si,N Ligands as Catalysts in Hydrolysis of Silanes

Preparation and Catalytic Properties of Graphene Oxide/ Phosphotungstic Acid Composites

Background: Cellulose structures are in stable crystallineform. The hydrolysis of cellulose to small reducing sugars is difficult, but essential for its utilization Objective: To investigate the effect of graphene oxide (GO) loading on the catalytic performance of phosphotungstic acid (HPW) for the catalyzed hydrolysis of cellulose, with the purpose to get high yield of total reducing sugar (TRS). Methods: Graphene oxide/phosphotungstic acid (GO/HPW) composites were prepared using a liquid-phase composite method. The materials were applied to catalyze hydrolysis of microcrystalline cellulose in 1-butyl-3-methylimidazole chloride ionic liquid ([Bmim]Cl). The samples were characterized by Powder X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), Field emission scanning electron micrographs (FE-SEM), pyridine IR and acid-base chemical titration. Results: The Brønsted acidic sites were the main source of acidity in the composites and its concentration was determined to be 0.96 mmol/g. With the use of the GO/HPW composite as catalysts for cellulose hydrolysis, TRS yield of 90.5 % was obtained. Conclusion: GO/HPW composites retained the functional groups of both materials. It was the Brønsted acidic sites in the materials that effectively promoted the cellulose hydrolysis reaction. The structures of GO/HPW with the agglomeration of HPW scattered on GO had high accessibility of acidic sites and fast mass transfer of the reducing sugars to the outside of the catalysts in time to prevent their further conversion into by-products. TRS yield of 90.5 % was obtained from the hydrolysis of cellulose catalyzed by the GO/HPW (1:1.5) composites at 115 ℃ for 4 h using catalysts to cellulose 1:1 ratio.

Silica-pyridine sulfonic acid catalyst for cellulose and glucose hydrolysis

An innovative catalyst was developed for the purpose of simplifying the manufacturing process of biofuels without the need for costly materials. The incorporation of pyridine sulfonic acid (PSA) into silica rice husk (RH) was achieved by two distinct strategies, resulting in the production of a heterogeneous catalyst. The first catalyst, RHAPSA@Dir, was prepared using the Sol-Gel technique through a one-pot synthesis approach. The second catalyst, RHAPSA@Ref, was created through post-synthesis means. BET analysis of RHAPSA@Dir showed a significant improvement in surface area to 416 m2/g, while RHAPSA@Ref only exhibited 48.2 m2/g. Upon conducting elemental research on both catalysts, it was observed that the presence of carbon, nitrogen, and sulfur was apparent. The thermal study conducted indicated that approximately 47–48% of organic matter was lost from the silica at the anticipated temperature. The SEM analysis of RHAPSA@Dir revealed that a minor level of pore arrangement was observed. Furthermore, the TEM analysis of RHAPSA@Dir demonstrated that a few particles exhibited spherical nano shapes that were clearly visible. Conversely, the SEM analysis of RHAPSA@Ref showed a rough and porous surface with large particles. Lastly, the TEM micrograph of RHAPSA@Ref revealed spherical particles with an approximate diameter of 6 nm. The use of electron microscopy revealed the presence of spherical nanostructures. Both cellulose and glucose underwent hydrolyzation over the catalysts within 2–6 h at 140 °C. The essential properties of both catalysts were their stability and reusability.

Hydrolysis of Carbonyl Sulfide in Blast Furnace Gas Using Alkali Metal-Modified γ-Al2O3 Catalysts with High Sulfur Resistance.

A carbonyl sulfide (COS) hydrolysis catalyst can play an efficient role in blast furnace gas (BFG), but the life of the catalyst is greatly shortened due to the presence of O2 and H2S in the atmosphere, so improving the sulfur resistance of the catalyst is the key to application. In this work, alkali metals Na and K modified γ-Al2O3 catalysts to improve COS hydrolysis efficiency and sulfur resistance by adding an alkaline center. Compared with γ-Al2O3 catalysts, the COS hydrolysis efficiency of the modified catalysts in the experiment was improved by 12% in the presence of H2S and O2. The main cause of catalyst sulfur poisoning is the presence of O2, which intensifies both the total amount of sulfur deposition and the proportion of sulfate. It is found that the NaOH/Al2O3 catalyst shows better sulfur resistance than the KOH/Al2O3 catalyst for two reasons: first, the support of Na can significantly improve the medium-strong alkaline site, which is the adsorption site of H2S. This is equivalent to increasing the "sulfur capacity" of H2S adsorption and reducing the impact of sulfur deposition on the main reaction. Second, the elemental sulfur is more easily produced on the NaOH/Al2O3 catalyst, but the sulfur is further oxidized to sulfate and sulfite on the KOH/Al2O3 catalyst. The molecular diameter of elemental sulfur is smaller than that of sulfate. Therefore, the NaOH/Al2O3 catalyst has better sulfur resistance.

Catalytic activity of two-dimensional cobalt-ZIF catalyst for NaBH4 hydrolysis

In this work, cobalt-ZIF catalysts were synthesized by water-based synthesis methods. Various hydrogen bond acceptor (tetramethylammonium bromide (TMAB), tetraethylammonium bromide (TEAB), tetrapropylammonium bromide (TPAB), tetrabutylammonium bromide (TBAB) and trimethylphenylammonium bromide (TMPAB)) were co-added during cobalt-ZIF catalyst synthesis procedures to promote the deprotonation of 2-methyl imidazole and the deprotonated 2-methyl imidazole was then further coordinated with cobalt ion to form a ZIF framework. Co-addition of TMPAB during synthesis resulted in 3D imperfect rhombic dodecahedrals with high surface area (432.3 m2/g), while, the rest of used hydrogen bond acceptors (TMAB, TEAB, TPAB and TBAB) provided 2D ZIF-L structure with relatively small surface area and pore volume. All synthesized cobalt-ZIF with different structures and morphologies were used as a catalyst for H2 generation by NaBH4 hydrolysis reaction. It was found that all 2D cobalt-ZIF structures exhibited higher hydrogen production rate than that of the 3D imperfect rhombic dodecahedral structure. This can be explained by the cushion-shaped cavity of a two-dimensional framework exhibiting higher flexibility which can promote more diffusion of reactants than the tetrahedral structure of a 3D-framework. X-ray absorption spectroscopy was used to investigate the electronic state of cobalt and to monitor the changing of cobalt probe atom during hydrolysis reaction. The electronic state of cobalt for all catalysts was Co2+ with the same tetrahedral symmetry. The lowering of pre-edge peaks of cobalt K edge XANES spectra during hydrolysis reaction indicated to distortion of the symmetry which is related to the reduction of the catalytic performance.

Synthesis of Trimetallic Nanoparticle (NiCoPd)-Supported Carbon Nanofibers as a Catalyst for NaBH4 Hydrolysis.

The generation of H2 via the catalytic hydrolysis of sodium borohydride (SBH) has promise as a practical and secure approach to produce H2, a secure and environmentally friendly energy source for the foreseeable future. In this study, distinctive trimetallic NiCoPd nanoparticle-supported carbon nanofibers (NiCoPd tri-NPs@CNFs) is synthesized via sol-gel and electrospinning approaches. The fabricated trimetallic catalysts show an excellent catalytic performance for the generation of H2 from the hydrolysis of SBH. Standard physicochemical techniques were used to characterize the as-prepared NiCoPd tri-NPs@CNFs. The results show that NiCoPd tri-NPs@CNFs is formed, with an average particle size of about 21 nm. When compared to NiCo bimetallic NP @CNFS, all NiCoPd tri-NPs@CNFs formulations demonstrated greater catalytic activates for the hydrolysis of SBH. The improved catalytic activity may be due in the majority to the synergistic interaction between the three metals in the trimetallic architecture. Furthermore, the activation energy for the catalytic hydrolysis of SBH by the NiCoPd tri-NPs@CNFs was determined to be 16.30 kJ mol-1. The kinetics studies show that the reaction is of a first order with respect to the catalyst loading amount and a half order with respect to the SBH concentration [SBH].

Development of reusable Ni/γ-Al2O3 catalyst for catalytic hydrolysis of waste PET bottles into terephthalic acid.

In order to efficiently recycle waste polyethylene terephthalate (PET) bottles, this study aimed to enhance the hydrolysis process to convert PET bottle into valuable terephthalic acid (TPA) by developing effective and reusable Ni/γ-Al2O3 catalysts. A series of Ni/γ-Al2O3 catalyst was prepared by the impregnation method with different Ni loadings (5-15 wt%) and was characterized by various techniques including XRD, SEM-EDX, and N2 adsorption-desorption. The prepared catalysts were employed in the catalytic hydrolysis of PET under varied influencing factors, namely reaction temperature (220-280 °C), reaction time (20-60 min), and Ni loading. The response surface methodology (RSM) was used to optimize the operating condition to produce the maximum TPA yield, and the optimal values were determined as follows: reaction temperature = 267.07 °C, reaction time = 48.54 min, and Ni loading = 12.90 wt%, giving the highest TPA yield of 97.06%. The R2, F-value, and P-value of the analysis of variance (ANOVA) were 0.9982, 424.96, and <0.0001, respectively, indicating a good fit of the model. The results from XRD and FTIR measurement of the produced TPA indicated the high purity and comparable chemical structures to the TPA standard. In addition, the 12.9Ni/Al catalyst exhibited high catalytic activity in repeated cycles of hydrolysis process of PET and could be regenerated by calcination to restore its catalytic activity. This finding could be a promising alternative for an effective TPA recovery from waste plastic bottles.

Unraveling the sulfur poisoning mechanism of N-doping KAl2O3 catalyst in simultaneous hydrolysis of COS and CS2 via experimental and theoretical study

The short lifetime and poor resistance to poisoning of hydrolysis catalysts restricted their application in the desulfurization of blast furnace gas. N doping was applied to enhance the low-temperature hydrolytic activity and stability of the catalysts, and the poisoning mechanisms of COS and CS2 were explored by a series of characterizations and DFT theoretical calculations. The results revealed that the N-modified catalyst could maintain 100 % COS conversion and more than 40 % CS2 conversion after 120 h reaction. The characterization results certified that reduced surface area, weakened surface basicity, and weakened COS and CS2 adsorption capacity were the main causes of catalyst poisoning. The deposited sulfur species on the catalyst were mainly monomeric sulfur and sulfate (Al2(SO4)3). The incorporation of N significantly reduced the production of Al2(SO4)3 and enhanced the protection of the Al active site by K, which in turn enhanced the resistance to poisoning. DFT theoretical calculations exhibited that the oxidation products of COS were mainly COSO2- and CO2SO-, while CS2 was easily converted to COS first and then further be oxidized. The addition of N made the oxidation intermediate species more difficult to generate, while the oxidation product SO2 was easier to desorb, which explained the improved catalyst resistance to poisoning.

Ni-BTC-derived CoP-NiCoP/NC microspheres as an efficient catalyst for NaBH4 hydrolysis

The development of a low cost, high performance and stable catalyst is an important prerequisite for the widespread application of efficient hydrogen production from sodium borohydride (NaBH4). Herein, Ni-BTC is derived into CoP-NiCoP/NC catalyst consisting of CoP-NiCoP nanorods and nitrogen-doped carbon (NC) microsphere by hydrothermal and gas-phase phosphorylation methods. The CoP-NiCoP/NC catalyst exhibits good catalytic activity, with a high hydrogen evolution rate of NaBH4 reaching 7052 mL·min−1·g−1 at 303 K, and an activation energy of only 35.57 kJ·mol−1. This is significantly better than most catalysts reported previously. In addition, the CoP-NiCoP/NC catalyst demonstrates good durability with 75 % of the original catalytic activity after 10 performance testing. This excellent catalytic performance is achieved thanks to its porous microsphere structural design and the cooperative effect between CoP and NiCoP. This catalyst with high catalytic performance and mild preparation conditions is promising for future actual applications.