Catalytic conversion of carbon dioxide (CO2) into value-added chemicals is of pivotal importance, well the cost of capturing CO2 from dilute atmosphere is super challenge. One promising strategy is combining the adsorption and transformation at one step, such as applying alkali solution that could selectively reduce carbonate (CO32-) as consequences of CO2 adsorption. Due to complexity of this system, the mechanistic details on controlling the hydrogenation have not been investigated in depth. Herein, Ru/TiO2 catalyst was applied as a probe to elucidate the mechanism of CO32- activation, in which with thermodynamic and kinetic investigations, a compact Langmuir-Hinshelwood reaction model was established which suggests that the overall rate of CO32- hydrogenation was controlled by a specific C-O bond rupture elementary step within HCOO- and the Ru surface was mainly covered by CO32- or HCOO- at independent conditions. This assumption was further supported by negligible kinetic isotope effects (kH/kD ≈ 1), similarity on reaction barriers of CO32- and HCOO- hydrogenation (ΔH‡hydr,Na2CO3 and ΔH‡hydr,HCOONa) and a non-variation of entropy (ΔS‡hydr ≈ 0). More interestingly, the alkalinity of the solution is certainly like a two sides in a sword and could facilitate the adsorption of CO2 while hold back catalysis during CO32- hydrogenation.

Reduction of carbon dioxide (CO2) by renewable electricity to produce multicarbon chemicals, such as ethylene (C2H4), continues to be a challenge because of insufficient Faradaic efficiency, low production rates, and complex mechanistic pathways. Here, we report that the rate-determining steps (RDS) on common copper (Cu) surfaces diverge in CO2 electroreduction, leading to distinct catalytic performances. Through a combination of experimental and computational studies, we reveal that C─C bond-making is the RDS on Cu(100), whereas the protonation of *CO with adsorbed water becomes rate-limiting on Cu(111) with a higher energy barrier. On an oxide-derived Cu(100)-dominant Cu catalyst, we reach a high C2H4 Faradaic efficiency of 72%, partial current density of 359 mA cm-2, and long-term stability exceeding 100 h at 500 mA cm-2, greatly outperforming its Cu(111)-rich counterpart. We further demonstrate constant C2H4 selectivity of >60% over 70 h in a membrane electrode assembly electrolyzer with a full-cell energy efficiency of 23.4%.

This work focuses on the comparison of H2 evolution in the hydrolysis of boron-containing hydrides (NaBH4, NH3BH3, and (CH2NH2BH3)2) over the Co metal catalyst and the Co3O4-based catalysts. The Co3O4 catalysts were activated in the reaction medium, and a small amount of CuO was added to activate Co3O4 under the action of weaker reducers (NH3BH3, (CH2NH2BH3)2). The high activity of Co3O4 has been previously associated with its reduced states (nanosized CoBn). The performed DFT modeling shows that activating water on the metal-like surface requires overcoming a higher energy barrier compared to hydride activation. The novelty of this study lies in its focus on understanding the impact of the remaining cobalt oxide phase. The XRD, TPR H2, TEM, Raman, and ATR FTIR confirm the formation of oxygen vacancies in the Co3O4 structure in the reaction medium, which increases the amount of adsorbed water. The kinetic isotopic effect measurements in D2O, as well as DFT modeling, reveal differences in water activation between Co and Co3O4-based catalysts. It can be assumed that the oxide phase serves not only as a precursor and support for the reduced nanosized cobalt active component but also as a key catalyst component that improves water activation.

Traditional cathode recycling methods have become outdated amid growing concerns for high-value output and environmental friendliness in spent Li-ion battery (LIB) recycling. Our study presents a closed-loop approach that involves selective sulfurization roasting, water leaching, and regeneration, efficiently transforming spent ternary Li batteries (i.e., NCM) into high-performance cathode materials. By combining experimental investigations with density functional theory (DFT) calculations, we elucidate the mechanisms within the NCM-C-S roasting system, providing a theoretical foundation for selective sulfidation. Utilizing in situ X-ray diffraction techniques and a series of consecutive experiments, the study meticulously tracks the evolution of regenerating cathode materials that use transition metal sulfides as their primary raw materials. The Li-rich regenerated NCM exhibits exceptional electrochemical performance, including long-term cycling, high-rate capabilities, reversibility, and stability. The closed-loop approach highlights the sustainability and environmental friendliness of this recycling process, with potential applications in other cathode materials, such as LiCoO2 and LiMn2O4. Compared with traditional methods, this short process approach avoids the complexity of leaching, solvent extraction, and reverse extraction, significantly increasing metal utilization and Li recovery rates while reducing pollution and resource waste.

The mixed ionic and electronic oxide LaNi0.6Fe0.4O3-δ (LNF) is a promising ceramic cathode material for solid oxide fuel cells. Since the reaction rate of oxygen interaction with the cathode material is extremely important, the present work considers the oxygen exchange mechanism between O2 and LNF oxide. The kinetic dependence of the oxygen/oxide interaction has been determined by two isotopic methods using 18O-labelled oxygen. The application of the isotope exchange with the gas phase equilibrium (IE-GPE) and the pulsed isotope exchange (PIE) has provided information over a wide range of temperatures (350-800 °C) and oxygen pressures (10-200 mbar), as each method has different applicability limits. Applying mathematical models to treat the kinetic relationships, the oxygen exchange rate (rH, atom × cm-2 × s-1) and the diffusion coefficient (D, cm2/s) were calculated. The values of rH and D depend on both temperature and oxygen pressure. The activation energy of the surface exchange rate is 0.73 ± 0.05 eV for the PIE method at 200 mbar, and 0.48 ± 0.02 eV for the IE-GPE method at 10-20 mbar; for the diffusion coefficient, the activation energy equals 0.62 ± 0.01 eV at 10-20 mbar for the IE-GPE method. Differences in the mechanism of oxygen exchange and diffusion on dense and powder samples are observed due to the different microstructure and surface morphology of the samples. The influence of oxygen pressure on the ratio of contributions of different exchange types to the total oxygen exchange rate is demonstrated. For the first time, the rate-determining step in the oxygen exchange process for LNF material has been identified. This paper discusses the reasons for the difference in the mechanisms of oxygen exchange and diffusion.

The electrocatalytic reduction of CO2 towards CO is one of the most desirable routines to reduce atmospheric CO2 concentration and maintain a global carbon balance. In this work, a novel porous NiCu-embedded ZIF-derived N-doped carbon nanoparticle (NiCu@NCNPs) catalyst has been identified as an active, highly selective, stable, and cost-effective catalyst in CO2 reduction. A CO selectivity as high as 100% has been achieved on NiCu@NCNPs which is the highest reported to date. The particle current density of CO on NiCu@NCNPs is around 15 mA cm-2 under the optimized potential at -0.9 V vs. RHE. The NiCu@NCNPs electrode also exhibits excellent stability during the five sequential CO2 electroreduction experiments. The superior catalytic performance of NiCu@NCNPs in CO2RR can be related to its microstructure with high electrochemical surface area and low electron transfer resistance. Furthermore, a kinetic analysis has shown the formation of intermediate *COOH is the rate-determining step in CO2RR towards CO. According to the results of density functional theory (DFT) calculations, a low Gibbs-free energy change (∆G) for the rate-determining step leads to the enhanced catalytic performance of CO2RR on NiCu@NCNPs.

Aromatic ring-opening process is well recognized as the rate-determining step for catalytic toluene degradation. In photocatalytic toluene degradation, the toxic intermediates with harmful effects may be generated. To clarify the precise reaction mechanism and control the toxic intermediates generation, a closely combined in situ DRIFTS and DFT calculation is utilized to address these important issues. We construct the BiOCl with oxygen vacancies (OVs) and reveal the structure of OVs. The defect level caused by oxygen vacancies could promote the light adsorption and charge separation, which further boosts the activation of ring-opening species and enhances the generation process of free radicals. The reaction energy barriers of four possible ring-opening processes on defective BiOCl (OVBOC) are all declined in comparison with perfect BiOCl (BOC). The existence of oxygen vacancies could smooth the rate-determining step so the ring-opening efficiency of photocatalytic toluene degradation is highly increased. Most importantly, the methyl species would be further oxidized and tend to open the benzene-ring at benzoic acid on BOC while the ring would be broken at the benzyl alcohol on OVBOC. These results indicate that the toluene degradation pathway is shortened via the surface OVs, which enables the production of radicals with high oxidation capability for the accelerated chain scission of the ring-opening intermediates. Finally, the efficiency of the key ring-opening process could be enormously improved and toxic intermediates are effectively restrained. The present work could provide new insights into the design of high-performance photocatalysts for efficient and safe degradation of VOCs in air.

Glycerol (GLY) aerobic oxidation in an aqueous solution is one of the most prospective pathways in biomass transformation, where the supported catalysts based on noble metals (mainly Au, Pd, Pt) are most commonly employed. Herein, Pt nanoparticles supported on rehydrated MgxAl1-hydrotalcite (denoted as re-MgxAl1-LDH-Pt) were prepared via impregnation-reduction method followed by an in situ rehydration process, which showed high activity and selectivity towards GLY oxidation to produce glyceric acid (GLYA) at room temperature. The metal-support interfacial structure and catalyst basicity were modulated by changing the Mg/Al molar ratio of the hydrotalcite precursor, and the optimal performance was achieved on re-Mg6Al1-LDH-Pt with a GLY conversion of 87.6% and a GLYA yield of 58.6%, which exceeded the traditional activated carbon and oxide supports. A combinative study on structural characterizations (XANES, CO-FTIR spectra, and benzoic acid titration) proves that a higher Mg/Al molar ratio promotes the formation of positively charged Ptδ+ species at metal-support interface, which accelerates bond cleavage of α-C-H and improves catalytic activity. Moreover, a higher Mg/Al molar ratio provides a stronger basicity of support that contributes to the oxidation of terminal-hydroxyl and thus enhances the selectivity of GLYA. This catalyst with tunable metal-support interaction shows prospective applications toward transformation of biomass-based polyols.

Limited comprehension of the reaction mechanism has hindered the development of catalysts for CO2 reduction reactions (CO2 RR). Here, the bimetallic AgCu nanocatalyst platform is employed to understand the effect of the electronic structure of catalysts on the selectivity and activity for CO2 electroreduction to CO. The atomic arrangement and electronic state structure vary with the atomic ratio of Ag and Cu, enabling tunable d-band centers to optimize the binding strength of key intermediates. Density functional theory calculations confirm that the variation of Cu content greatly affects the free energy of *COOH, *CO (intermediate of CO), and *H (intermediates of H2 ), which leads to the change of the rate-determining step. Specifically, Ag96 Cu4 reduces the free energy of the formation of *COOH while maintaining a relatively high theoretical overpotential for hydrogen evolution reaction(HER), thus achieving the best CO selectivity. While Ag70 Cu30 shows relatively low formation energy of both *COOH and *H, the compromised thermodynamic barrier and product selectivity allows Ag70 Cu30 the best CO partial current density. This study realizes the regulation of the selectivity and activity of electrocatalytic CO2 to CO, which provides a promising way to improve the intrinsic performance of CO2 RR on bimetallic AgCu.

Photo-thermo catalysis utilizing light has been a promising strategy to improve the conventional thermal catalytic activity and attracts great attention nowadays. However, how heat works in synergy with light radiation is still unclear. This Concept article is trying to clarify the specific contents via summarizing the kinetic studies including 1) proposing elementary steps through pressure dependence studies, 2) estimating reaction barriers through measuring the apparent activation energies and 3) assigning the kinetically relevant step(s) with kinetic isotope effects (KIE) as well as 4) exploring the relationship of the reaction rate with the light excitation wavelength and light intensity. The challenges in kinetic studies such as describing the light-induced carrier transfer process, the surface temperature under light illumination as well as reaction intermediates were discussed at the same time. Finally, an outlook about kinetic studies in clarifying the photo-thermo catalysis reaction mechanism was proposed.