H2O Dissociation Research Articles

Supercritical water co-gasification of waste R134a and plastics to produce valuable chemicals and fuels: ReaxFF reactive molecular dynamic simulation

Supercritical water gasification of waste hydrofluorocarbon refrigerants was an effective treatment technology, but there is a problem of high yield of fluorine-containing products with complex types. Plastic has the potential to provide sufficient H atoms as hydrogen donor to facilitate defluorination of fluorine-containing products. In this study, ReaxFF reactive molecular dynamic simulation and density functional theory calculation were used to investigate the supercritical water co-gasification (SCWCG) mechanism of R134a and low-density polyethylene (LDPE). The results showed that the decomposition of LDPE was the initial reaction of SCWCG, the generated radicals promoted the dissociation of R134a and H2O. The dominant SCWCG products were valuable hydrocarbons, H2, CO and HF. The present of LDPE promoted the defluorination reaction of fluorine-containing products from the dissociation of R134a, reduced the yield of fluorine-containing products, and greatly promoted the yields of H2, HF, CO and hydrocarbon products. 99% of F atoms in R134a can be converted to HF, which indicated that plastics participating in supercritical water gasification of R134a has excellent defluorination effect. This study provided an efficient and potential route to conduct waste HFC refrigerants into valuable chemicals and fuels.

There are plenty of atomic vacancies at the bottom

Atomic vacancies are primordial for controlling the photocatalytic activity of perovskites. On the one hand, they are useful adsorption sites and help narrow the band gap, but they may also trap the electron-hole pair created after light absorption. Its precise control, although essential, is hardly achieved with traditional methods. In this work, an alternative experimental approach is employed to finely control the atomic vacancy population of SrTiO3 nanoparticles for application in the photodegradation of methylene blue. The atomic vacancies are created through Au7+ irradiation using different fluencies. The irradiated samples exhibit a photodegradation efficiency up to three times higher than the case without irradiation. X-ray absorption spectroscopy (XAS) measurements show that the local atomic order decreases with the ion irradiation, but it increases again after the photodegradation reaction. After the reaction, new surface chemical components appear in the X-ray photoelectron spectroscopy (XPS) measurements. These come due to the atomic vacancy diffusion from the inner to the surface region, as explained by Density Function Theory (DFT) calculations. The improvement in the photodegradation results is closely related to these atomic vacancies at the surface, as demonstrated by in situ Small Angle X-Ray Scattering (SAXS) measurements, and these enable the H2O dissociation, thus forming radicals that desorb for degrading the methylene blue molecule.

Unlocking the Effects of the RuCo Alloy Ratio on Alkaline Hydrogen Production.

Understanding the interaction between Ru and Co components and the alloy ratio effects on the catalytic process is a technical challenge that requires a precise alloy structural design. This study proposes an effective stepwise annealing method for the construction of RuCo alloy-based electrocatalysts with varied Ru:Co ratios. Interestingly, as the concentration of Co in the first-step pyrolysis products increases, the secondary pyrolysis results in RuCo composites undergoing a transition from incomplete alloying to alloy ratios of 1:1, 1:2, and 1:8. When the alloy ratio is 1:1, more Run+ and Co0 transform into Ru0 and Co2/3+. In 1 M KOH, RuCo-0.6/NC demonstrates outstanding catalytic performance and durability even superior to that of commercial Pt/C, delivering a lower overpotential of 16 mV at 10 mA cm-2. DFT calculations reveal that the fast H2O dissociation and moderate H adsorption guarantee the superior activity of RuCo.

CeO2‐Accelerated Surface Reconstruction of CoSe2 Nanoneedle Forms Active CeO2@CoOOH Interface to Boost Oxygen Evolution Reaction for Water Splitting

AbstractInterface engineering is an efficient strategy to create high‐performance electrocatalysts for water splitting. In the present work, CeO2@CoSe2 nanoneedle on carbon cloth (CeO2@CoSe2/CC) demonstrates high efficiency for oxygen evolution reaction (OER) and water splitting. CeO2 with abundant O vacancies facilitates the adsorption of OH− and boosts the reconstruction of CoSe2 into CoOOH at lower potentials. The in situ generated active CeO2@CoOOH heterointerface upshifts the d‐band center of Co site, thereby decreasing the free energy of rate‐determining step (RDS) (*O to *OOH) during the OER process. It delivers a low OER overpotential of 245 mV at 10 mA cm−2. CeO2@CoSe2/CC is also found to be active for hydrogen evolution reaction (HER, 138 mV overpotential at 10 mA cm−2), profiting from CeO2‐facilitated *H2O dissociation and *H adsorption on CoSe2. The overall water splitting is achieved over the CeO2@CoSe2/CC bifunctional electrode with a low electrolysis voltage of 1.54 V at 10 mA cm−2. This work offers valuable insights into CeO2‐assisted surface reconstruction as well as provides water electrolysis catalysts through interface engineering.

Satellite Pd Single-Atom Embraced AuPd Alloy Nanoclusters for Enhanced Hydrogen Evolution.

The fabrication of hybrid active sites that synergistically contain nanoclusters and single atoms (SAs) is vital for electrocatalysts to achieve excellent activity and durability. Herein, we develop a ligand-assisted pyrolysis strategy using nanoclusters (Au4Pd2(SC2H4Ph)8) with alloy cores and protected ligands to build AuPd cluster sites embraced by satellite Pd SAs. In the thermal drive control process, different thermodynamic properties of the alloy atoms and the confinement effects of organic ligands allow for the mild spillover of the single-component metal Pd, resulting in the formation of AuPd alloy nanoclusters tightly encompassed by isolated Pd atoms. Experiments and theoretical calculations indicated that the satellite Pd atoms can optimize the electronic structure of the AuPd nanoclusters and Au sites in the alloy to facilitate the adsorption and dissociation of H2O, thus enhancing the hydrogen evolution reaction (HER) activity. The optimal AuPdNCs/PdSAs-600 exhibits outstanding electrocatalytic activity toward HER, with overpotentials of 21 and 38 mV at 10 mA cm-2 in acidic and alkaline media, respectively. Moreover, the mass activity and turnover frequency of AuPdNCs/PdSAs-600 are one order of magnitude higher than those of commercial Pd/C and Pt/C catalysts. This facile strategy for constructing hybrid catalytic centers using ligand-protected nanoclusters provides efficient insights for the further design of nanocluster-based electrocatalysts synergized by SAs.

AMn2O4 (A = Ni, Co, Cu) oxygen carrier chemical looping reforming of benzene: Migration pathways of reactive oxygen species by experimental and DFT investigations

Chemical looping reforming (CLR) provides a novel solution for clean and efficient utilization of biomass tar. The versatility of oxygen carrier (OC) is essential for improving reforming efficiency. The properties of Mn-based spinel OCs (AMn2O4, A = Ni, Co, Cu) were investigated in the CLR process using benzene as a tar model compound. Detailed characterization and experimental results demonstrate the excellent structural stability of Mn-based spinel. The NiMn2O4 showed the most prominent reforming effect on benzene with the highest conversion of 95.77 % at 850 °C, S/C = 1.0, and WHSV = 3.0 h−1. After 40 cycles, NiMn2O4 and CoMn2O4 maintained significant catalytic activity for benzene reforming, achieving conversions of 92.96 % and 90.07 %, respectively, in the final cycle. Density functional theory (DFT) calculations demonstrate that the addition of H2O increases the activity of NiMn2O4. Compared to benzene adsorption alone, the adsorption energy decreased from −2.20 eV to −2.54 eV after the addition of H2O. The migration path of NiMn2O4 (100) reactive oxygen species in the presence or absence of H2O is directly demonstrated. In the absence of H2O, the activation energy barrier for direct oxidation of C6H5* by NiMn2O4 lattice oxygen is dominant (0.98 eV), but OH* produced by dissociation of H2O exhibits high activity, and oxidation of C6H5* to produce the key intermediate product C6H5O* has an activation energy barrier of only 0.35 eV. In addition, H2O has a predominant role in the replenishment of oxygen vacancies. The elucidation of the oxygen migration mechanism provides new guidance for the design of efficient OCs for catalytic oxidation.

Multisite Pt/H2Ti2O5-TiO2 catalyst for formaldehyde oxidation

The development of multisite catalysts that simultaneously satisfy compositional, spatial arrangement and functional requirements remains a significant challenge. Herein, we report a supported Pt catalyst on surface hydroxyl- and oxygen-vacancy-rich H2Ti2O5/TiO2 composite nanotubes for formaldehyde (HCHO) oxidation. Our study demonstrates that H2Ti2O5/TiO2 nanotubes can be prepared by a hydrothermal method and in particular, using Na2[Pt(OH)6] as a metal precursor yields ultrasmall and uniformly distributed Pt nanoparticles on the nanotube surface. In situ diffuse reflectance infrared Fourier transform spectroscopy analyses reveal that HCHO oxidation over the Pt/H2Ti2O5-TiO2 catalyst occurs via a cooperative catalysis mechanism: Pt facilitates the splitting of O2, surface hydroxyl group on H2Ti2O5 serves as HCHO adsorption site and oxygen vacancy on the TiO2 surface promotes the dissociation of H2O to generate active OH species. Consequently, the Pt/H2Ti2O5-TiO2 catalyst exhibits an impressively high mass-specific reaction rate of 118.0 μmol gPt−1 s−1 and excellent stability, outperforming previously reported HCHO oxidation catalysts.

The Interfacial Ni/Fe─O─Y Bonds Contribute to High-Efficiency Water Splitting.

Developing economical and efficient electrocatalysts is critical for hydrogen energy industrialization through water electrolysis. Herein, a novel dual-site synergistic NiFe/Y2O3 hybrid with abundant interfacial Ni/Fe─O─Y bonds is designed by density functional theory (DFT) simulations. In situ Raman spectra combined with DFT calculations reveal that the interfacial Ni/Fe─O─Y units greatly promote H2O dissociation and optimize the adsorption of both H* and oxygen species, achieving excellent activity and durability for hydrogen evolution reaction. As expected, NiFe/Y2O3 exhibits a low overpotential of 27 mV at 10 mA cm-2 and robust stability of over 200 h at 1000 mA cm-2, and also outstanding water splitting performance with a low cell voltage of 1.64 V at 100 mA cm-2, showing significant potential for real-world applications.

Integrated “Two‐in‐One” Strategy for High‐Rate Electrocatalytic CO2 Reduction to Formate

AbstractThe electrochemical CO2 reduction reaction (ECR) is a promising pathway to producing valuable chemicals and fuels. Despite extensive studies reported, improving CO2 adsorption for local CO2 enrichment or water dissociation to generate sufficient H* is still not enough to achieve industrial‐relevant current densities. Herein, we report a “two‐in‐one” catalyst, defective Bi nanosheets modified by CrOx (Bi−CrOx), to simultaneously promote CO2 adsorption and water dissociation, thereby enhancing the activity and selectivity of ECR to formate. The Bi−CrOx exhibits an excellent Faradaic efficiency (≈100 %) in a wide potential range from −0.4 to −0.9 V. In addition, it achieves a remarkable formate partial current density of 687 mA cm−2 at a moderate potential of −0.9 V without iR compensation, the highest value at −0.9 V reported so far. Control experiments and theoretical simulations revealed that the defective Bi facilitates CO2 adsorption/activation while the CrOx accounts for enhancing the protonation process via accelerating H2O dissociation. This work presents a pathway to boosting formate production through tuning CO2 and H2O species at the same time.

Vanadium-Doped Heterointerfaced Ni3N-MoOx Nanosheets with Optimized H and H2O Adsorption for Effective Alkaline Hydrogen Electrocatalysis.

Nickel (Ni)-based materials represent a compelling avenue as platinum alternatives in the realm of alkaline hydrogen electrocatalysis. However, conventional nickel nitrides (Ni3N) have long been hindered by sluggish hydrogen evolution kinetics in alkaline environments, owing to inadequate adsorption strengths of both hydrogen and water molecules. Herein, a novel approach is presented involving the design of vanadium (V)-doped Ni3N/MoOx heterogeneous nanosheets (V-Ni3N@MoOx), engineered to achieve optimized adsorption strengths for hydrogen evolution and oxidation reactions (HER/HOR). Theoretical insights underscore the superior catalytic performance of this composite, attributed to a synergistic interplay between unique V doping and the heterointerfaced structure. This synergistic effect not only fine-tunes the electronic structure, establishing an optimal d band center to mitigate proton over-bonding, but also ameliorates the energy barrier through enhanced H2O dissociation capability. Consequently, V-Ni3N@MoOx manifests remarkable catalytic activities, evincing an overpotential of 56mV at 10mAcm-2 for HER and an exchange current density of 1.91mAcm-2 for HOR in alkaline media. Notably, the stability assessment reveals the enduring performance of V-Ni3N@MoOx for HER/HOR, exhibiting no activity decay over extended operational durations. This study underscores the efficacy of heterogeneous interface modulation as a transformative strategy in designing Ni-based materials for alkaline hydrogen electrocatalysis.

Interface‐Triggered Spin‐Magnetic Effect in Rare Earth Intraparticle Heterostructured Nanoalloys for Boosting Hydrogen Evolution

AbstractRare earth (RE) elements are attractive for spin‐magnetic modulation due to their unique 4 f electron configuration and strong orbital couplings. Alloying RE with conventional 3d transition‐metal (TM) is promising for the fabrication of advanced spin catalysts yet remains much difficulties in preparation, which leads to the mysteries of spin‐magnetic effect between RE and 3d TM on catalysis. Here we define a solid‐phase synthetic protocol for creating RE‐3d TM‐noble metal integrated intraparticle heterostructured nanoalloys (IHAs) with distinct Gd and Co interface within the entire Rh framework, denoted as RhCo−RhGd IHAs. They exhibit interface‐triggered antiferromagnetic interaction, which can induce electron redistribution and regulate spin polarization. Theoretical calculations further reveal that active sites around the heterointerface with weakened spin polarization optimize the adsorption and dissociation of H2O, thus promoting alkaline hydrogen evolution catalysis. The RhCo−RhGd IHAs show a small overpotential of 11.3 mV at 10 mA cm−2, as well as remarkable long‐term stability, far superior to previously reported Rh‐based catalysts.

Interface-Triggered Spin-Magnetic Effect in Rare Earth Intraparticle Heterostructured Nanoalloys for Boosting Hydrogen Evolution.

Rare earth (RE) elements are attractive for spin-magnetic modulation due to their unique 4 f electron configuration and strong orbital couplings. Alloying RE with conventional 3d transition-metal (TM) is promising for the fabrication of advanced spin catalysts yet remains much difficulties in preparation, which leads to the mysteries of spin-magnetic effect between RE and 3d TM on catalysis. Here we define a solid-phase synthetic protocol for creating RE-3d TM-noble metal integrated intraparticle heterostructured nanoalloys (IHAs) with distinct Gd and Co interface within the entire Rh framework, denoted as RhCo-RhGd IHAs. They exhibit interface-triggered antiferromagnetic interaction, which can induce electron redistribution and regulate spin polarization. Theoretical calculations further reveal that active sites around the heterointerface with weakened spin polarization optimize the adsorption and dissociation of H2O, thus promoting alkaline hydrogen evolution catalysis. The RhCo-RhGd IHAs show a small overpotential of 11.3 mV at 10 mA cm-2, as well as remarkable long-term stability, far superior to previously reported Rh-based catalysts.

D-Band Center Engineering of Nickel Nanoparticles Accelerates Water Dissociation for Hydrogen Evolution in Neutral NaCl Solution.

While Pt is highly efficient for hydrogen evolution reaction (HER), its widespread use is limited by scarcity and high cost. Herein, a vertically aligned electrocatalyst is present comprising Ni3S2 nanotube arrays (NTAs) and Ni nanoparticles (NPs) (Ni3S2/Ni NTAs) for neutral HER. In a neutral 4 wt.% NaCl solution (pH = 7), the Ni3S2/Ni NTAs achieves a current density of 100mA cm-2 at a low overpotential of 540mV, outperforming both Ni3S2 NTAs and Ni NTAs and even the commercial Pt plate. The hollow tubular structure offers ample mass transfer channels, and strong electronic interaction between Ni3S2 and Ni is observed. Theoretical studies reveal that the lowered d-band center (ɛd) of Ni 3d orbital significantly reduces the activation energy for H2O dissociation and facilitates the movement of an H atom in H2O away from OH to form a transition state, consequently promoting H2 evolution. When Ni3S2/Ni NTAs is used as the cathode in a two-electrode diaphragm-free electrolyzer with a RuSnTi anode, efficient H2 production and energy-saving Cl2 evolution are achieved. This work highlights the potential of uniquely structured electrocatalysts for HER in neutral NaCl solutions.

MXene quantum dots-Co(OH)2 heterojunction stimulated Co2+δ sites for boosted alkaline hydrogen evolution

Persevering structural stability of the active species after phase reconfiguration poses a key challenge for various sustainable catalytic systems. In this study, we construct a robust β-Co(OH)2 electrocatalyst via self-adaptive coordination of MXene quantum dots (MQDs) during phase transition from the Co2(OH)3Cl precursor to β-Co(OH)2 (MQDs/β-Co(OH)2/Co foam). The heterojunction induced the excellent electron transfer, causing the lattice strain of β-Co(OH)2, and the accumulated electrons at the MQDs end regulated the electronic density of Co sites (Co2+δ), reversing the structural instability of β-Co(OH)2 within the applied reduction potential range. Furthermore, density functional theory calculation confirms the role of well-matched heterogeneous interfaces in HER. The result shows the high-valance Co2+δ sites promote adsorption and dissociation of H2O, increasing proton supply and accelerating reaction rate. Concurrently, MQDs facilitate the adsorption of hydrogen intermediates and H2 generation. Our architected catalyst exhibited exceptional alkaline hydrogen evolution reactions (HERs) performance (91 mV@10 mA cm−2) and superior stability outperforms most reported β-Co(OH) 2-based catalysts. Our work demonstrates the efficacy of MQDs as co-catalysts in enhancing the activity and structural stability of catalysts.

OH Regulator of Amorphous CrOx on Defect-Rich Ultrafine Pd Nanowires Boosts Electrocatalytic Ethanol Oxidation.

Reasonable construction of high activity and selectivity electrocatalysts is crucial to achieve efficient ethanol oxidation reaction (EOR). However, the oxidation of ethanol tends to produce CO species that poison the active centers of the EOR electrocatalysts. Herein, a unique amorphous CrOx-protected defect-rich ultrafine Pd nanowires (CrOx-Pd NWs) is developed. On the one hand, the CrOx layer can act as a protective layer to maintain the structure of the nanowire. On the other hand, it can play the role of OH regulator to optimize the adsorption energy barrier of intermediate species in Pd nanowire, thereby enhancing the ability of the catalyst to resist CO poisoning. The CrOx-Pd NWs exhibit excellent EOR performance with 3.64 times higher mass activity and 50mV lower CO electro-oxidation potential than commercial Pd black. The results show that the CrOx layer promotes the dissociation of H2O into OHads, while the CrOx transfers electrons to neighboring Pd atoms optimizing the electronic configuration of Pd, thus selectively oxidizing ethanol to acetate and preventing the formation of toxic *CO. This work provides an effective strategy for the synthesis of nanowire materials with oxide/metal interfaces and offers new ideas for the design of catalysts that can efficiently drive EOR.

Constructing Hydrangea-Like Iron-Cobalt Phosphides via Boron-Assisted Strategy as an Efficient Catalyst for Water Splitting at High Current Density.

Finding suitable bifunctional catalysts for industrial hydrogen production is the key to fully building a hydrogen energy society. In this study, we present a novel approach to modifying the surface morphology of electrodeposited cobalt phosphide (CoP). Specifically, we have developed a method to create a hydrangea-like structure of bimetallic cobalt-iron phosphide (B-CoFeP@CoP) through ion-exchange and NaBH4-assisted strategies. This catalyst exhibited excellent bifunctional catalytic capability at high current densities, achieving a current density of 500 mA cm-2 at a small overpotential (387 mV for OER and 252 mV for HER). When assembled into an OWS electrolyzer, this catalyst showed a fairly low cell voltage (≈1.88 V) at 500 mA cm-2 current density., Furthermore, B-CoFeP@CoP shows ceaseless durability over 120 h in both freshwater and seawater with almost no change in the cell voltage. A combined experimental and theoretical study identified that the unique hydrangea-like structure provided a larger electrochemically active surface area and more effective active sites. Further analysis indicates that during the OER process, phosphides ensure that bimetallic active sites adsorb more OOH * intermediates and further DFT calculations showed that B-Fe2P and B-Co2P acted as active centers for dissociation of H2O and desorption of H2, respectively, to synergistically catalyze the HER process.

Rationally Designed Mo/Ru-Based Multi-Site Heterogeneous Electrocatalyst for Accelerated Alkaline Hydrogen Evolution Reaction.

The rational design of multi-site electrocatalysts with three different functions for facile H2O dissociation, H-H coupling, and rapid H2 release is desirable but difficult to achieve. This strategy can accelerate the sluggish kinetics of the hydrogen evolution reaction (HER) under alkaline conditions. To resolve this issue, a Mo/Ru-based catalyst with three different active sites (Ru/Mo2C/MoO2) is rationally designed and its performance in alkaline HER is evaluated. The experimental results and density functional theory calculations revealed that, at the heterogeneous Mo2C/MoO2 interface, the higher valence state of Mo (MoO2) and the lower valence state of Mo (Mo2C) exhibited strong OH- and H-binding energies, respectively, which accelerated H2O dissociation. Moreover, the interfacial Ru possessed an appropriate hydrogen binding energy for H-H coupling and subsequent H2 evolution. Thus, this catalyst significantly accelerated the Volmer step and the Tafel step and, consequently, HER kinetics. This catalyst also demonstrated low overpotentials of 19 and 160mV at current densities of 10 and 1000mA cm-2, respectively, in alkaline media and long-term stability superior to that of most state-of-the-art alkaline HER electrocatalysts. This work provides a rational design principle for advanced multi-site catalytic systems, which can realize multi-electron electrocatalytic reactions.

Improved HER/OER Performance of NiS2/MoS2 Composite Modified by CeO2 and LDH.

In recent years, there has been significant interest in transition-metal sulfides (TMSs) due to their economic affordability and excellent catalytic activity. Nevertheless, it is difficult for TMSs to achieve satisfactory performance due to problems such as low conductivity, limited catalytic activity, and inadequate stability. Therefore, a catalyst with a heterostructure constituted of a nickel-iron-layered double hydroxide, nickel sulfide, molybdenum disulfide, and cerium dioxide was designed. At the current density of 10 mA cm-2 in an alkaline solution, the catalyst exhibits a HER overpotential of 116 mV. In addition, an overpotential of 235 mV@150 mA cm-2 was displayed for OER. The catalyst showed a good retention rate (94.7% for HER, 98.6% for OER) after 160 h stability tests. The excellent electrochemical performance is attributed to the following points: 1. The self-supporting three-dimensional hierarchical structure provides abundant sites, fast ion diffusion channels, and electron transfer paths, and ensures structural stability. 2. The strong interfacial electron interaction between Ni3S2/MoS2 heterojunction and NiFe-LDH improves the OER reaction kinetics. 3. The Ce3+ and oxygen vacancies in CeO2 promote the dissociation of H2O and promote the HER reaction kinetics. This approach paves the way for developing highly efficient electrocatalysts for various electrochemical applications.

A strong metal-support interaction strategy for enhanced proton-coupled electron transfer and promoted photocatalytic H2O2 production in pure water

Proton-coupled electron transfer (PCET) is a key factor in determining the H2O2 production efficiency from oxygen reduction reaction (ORR) or direct H2/O2 reaction, which usually requires the aid of proton donors including alcohols. Here, we report a strong metal-support interaction (SMSI) strategy to facilitate the PCET process of a typical Pd/TiO2 photocatalyst for photocatalytic ORR into H2O2 production in pure water. Compared to conventional Pd/TiO2 photocatalysts, the Pd/TiO2 photocatalyst with SMSI between Pd and TiO2 (Pd/TiO2-850H) promotes photocatalytic H2O2 production in pure water by 4.21-fold, which can be ascribed to that the SMSI simultaneously promotes the H2O dissociation and the photogenerated charge transfer from TiO2 to Pd catalyst, enabling highly efficient proton transfer to be participated into converting •O2- to H2O2. Moreover, the formation of TiO2-x overlayer caused by SMSI suppresses the H2O2 decomposition and stabilizes Pd NPs, finally achieving an H2O2 production rate of 4.10 mmol g−1 h−1, which surpasses most metal/TiO2 photocatalytic system.

Enhancement and sulfur poisoning mechanism of Ce doped ZrO2 catalyst in COS hydrolysis at low-temperature

In order to achieve efficient and longer-lifespan removal of carbonyl sulfide (COS), a high-performance catalyst for hydrolysis is needed urgently. In this study, Ce doped ZrO2 oxides are used to remove COS with or without H2O. The results showed that the doping of Ce significantly improves the removal of COS by ZrO2 and obtains a sulfur capacity of 155.4 mgS/g at 70 °C, but there is still accompanied by sulfur poisoning. The characterization reveals that CeO2 has a cubic phase, ZrO2 has a mixed phase of tetragonal and monoclinic, and Ce-doped Zr with different ratio of Ce/Zr forms a Ce-Zr solid solution. Ce and Ce-Zr oxides have Ce3+/Ce4+ pairs, adsorbed oxygen species and surface oxygen vacancies, while ZrO2 has adsorbed oxygen and surface oxygen vacancies, the presence of which can promote the dissociation of H2O and surface adsorption of COS. ZrO2 has abundant medium-strong basicity while CeO2 has abundant weak and strong basicity, and different proportions of Ce/Zr adjust the surface basic strength, basic amount and surface redox property of Ce-Zr solid solution, which changes the adsorption and hydrolysis of COS and H2O and related oxidation reactions on Ce and Zr, thereby changing the sulfur poisoning. Ce has abundant –OH groups, which can rapidly adsorb COS, leading to hydrolysis and direct oxidation of COS in the absence of H2O, while the OH groups on ZrO2 promote the hydrolysis of COS to H2S. Although suitable Ce-doped ZrO2 improves the removal efficiency of COS, it still inevitably leads to the sulfur poisoning, but the presence of Zr could change the sulfation degree of CeO2 and the Claus reaction.