Surfaces and Interfaces
·
2024
·
IF 5.7
Zhiwei Zou,Hongxiang Zhang,Xuefeng Pan,Hui Shen,Jianying Yu,Tengfei Guo,Yonghao Wang
Electrocatalytic reduction of nitrate (NO 3 - ) to ammonium (NH 4 + ) is an environment friendly approach for treating nitrogen-containing wastewater. Consequently, electrocatalysts capable of effectively and selectively reducing NO 3 - to NH 4 + receives growing attention. However, Cu-based catalysts demonstrate limited efficiency and the drawback of generating toxic NO 2 - though it is prevalent in the field of electrocatalytic reduction of NO 3 - (NO 3 RR). In this work, a CuNi alloy was synthesized on a Co foil through electrodeposition (marked as CuNi@Co) and its electrocatalytic performance for NO 3 RR was evaluated. XRD, EDS mapping and XPS characterization indicate CuNi exists with alloy state. Electrocatalytic experiments demonstrate that CuNi@Co exhibits an exceptional FE NH3 of 99.12% at -0.64 V (vs. RHE). Importantly, no detrimental NO 2 - generated during NO 3 RR process because the reduction rate from NO 2 - to NH 4 + is faster than that from NO 3 - to NO 2 - . Mechanistic analysis suggests that Cu serves as a ‘reservoir’ to provide electrons to facilitate the reduction of NO 3 - to NO 2 - during NO 3 RR process and the synergistic effect of Ni and Cu promotes more active hydrogen (H*) to participate the reduction process of NO 2 - to NH 4 + not H 2 generation, ultimately improving FE NH3 . This work elucidates the role of electrons and H* in electrocatalytic nitrate reduction to ammonium for CuNi alloy, providing new insights into the reduction process of NO 3 RR for Cu-based materials.
研究领域:
环境科学
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电催化
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2025
·
IF 7.5
Hong-Hui Gong,Xian-Yong Wei,Wen-Long Mo,Zhi-Min Zong,Guang-Hui Liu,Pei Liu,Kun-Peng Jiao
NiCs/Al 2 O 3 with medium-strong alkaline and the contents of Ni and Cs of 26.55 wt% and 0.02 wt%, respectively, was prepared by a three-step method and characterized with multiple tools. Oxydibenzene (ODB) and benzyloxybenzene (BOB) were used as low-rank coal-related model compounds and their catalytic hydroconversion (CHC) were investigated over NiCs/Al 2 O 3. Under mild conditions (MCs), NiCs/Al 2 O 3 can effectively activate H 2 to biatomic active hydrogen (H···H) and part of H···H can be effectively split to relative mobile H - and immobile H + on the NiCs/Al 2 O 3 surface. Both ODB and BOB can be completely converted and full hydrogenation (FH) of the benzene ring (BR) in −O-BR is the first step for the CHC of both ODB and BOB via H···H transfer to the BR under MCs. Subsequently, H - transfer to an ipso -carbon (IC) in the resulting oxydicyclohexane from the FH of ODB cleaves an −O-CH< bond to produce cyclohexane (CH I ) and cyclohexyloxy anion (CHOA), which abstracts H + from H···H to afford cyclohexanol (CH II ) followed by H - transfer to the IC in CH II and subsequent HO – release to yield CH I . As a result, CH I is the only final product from the CHC of ODB. In contrast, H - transfer preferentially proceeds to the carbon atom in the –CH 2 - of the resulting benzyloxycyclohexane from the FH of the BR in −O-BR of BOB to produce toluene and CHOA followed by the FH of toluene to get methylcyclohexane and the H + abstraction by CHOA from H···H to obtain CH II . Moreover, NiCs/Al 2 O 3 shows a distinguished recyclability and repeatability.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
Surfaces and Interfaces
·
2024
·
IF 5.7
Hele Hua,Nan Zhang,Zhidan Wang,Rui Li,Yunfang Wang,Jianxin Liu,Peide Han,Caimei Fan,Yawen Wang
Electrocatalytic NO 3 − reduction reaction (NO 3 RR) has attracted much attention as a promising NH 3 synthesis pathway, and Cu-based catalysts have been proven to lead to advantages in nitrate reduction . However, the active hydrogen (H*) produced by the Cu-based catalyst is insufficient to satisfy the hydrogenation process of the NO 3 RR intermediate, resulting in a large generation of NO 2 − . In this paper, the Co(OH) 2 /Cu 2 O heterojunction was constructed to improve the kinetics of H 2 O dissociation to generate H* and Co(OH) 2 /Cu 2 O (5.87 %) showed lower faradaic efficiency (FE) of NO 2 − than Cu 2 O (50.95 %). Mechanistic studies reveal that the introduction of Co(OH) 2 can help Cu 2 O lower the energy barrier of H 2 O dissociation, greatly boosting the supply of active hydrogen (H*). Not only that, but the reaction energy barriers of *NO to *NOH can be greatly reduced. The final twofold reason works together to greatly improve the efficiency of hydrogenation of NO 2 − , largely solving the problem of FE reduction due to the delayed consumption of NO 2 − , thus realizing improved performance.
研究领域:
化学
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材料科学
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催化
✓ 已验证
产品关联
DOI
高影响因子
ChemCatChem
·
2021
·Vol. 13
·期 23
·4937-4947
·
IF 5.686
Chenglin Miao,Fengyu Zhang,Luoyu Cai,Tianli Hui,Junting Feng,Dianqing Li
Graphical Two kinds of electron-rich interface sites are clearly identified in ultrathin Pt/CoAl-LDH catalyst. A series of technologies found that the Pt−V O −Co δ+ interface site can change the adsorption mode of C=O bond, and the Pt−V Co −OH δ− interface site facilitates the mobility of active hydrogen. Therefore, the ultrathin catalyst exhibits enhanced COL yield under the synergistic effect of the dual interface sites. Focusing on the simultaneous enhancement of activity and selectivity in α, β-unsaturated aldehyde hydrogenation, we designed and prepared an ultrathin CoAl-LDH supported Pt catalyst. A series of technologies revealed the ultrathin CoAl-LDH support possesses the characteristic of dual defects, oxygen vacancy (V O ) and cobalt vacancy (V Co ). Then, two kinds of vacancy related interface sites were identified, namely Pt−V O −Co δ+ and Pt−V Co −OH δ− . Compared with the bulk catalyst, the ultrathin catalyst exhibits both enhanced intrinsic activity and C=O bond selectivity under the synergistic effect of the dual interface sites. Specifically, the Pt−V O −Co δ+ interface site changes the adsorption mode of cinnamaldehyde and promotes the activation of C=O bonds, thus leading to the improved cinnamyl alcohol selectivity. The H atoms of the Pt−V Co −OH δ− interface site participate in the hydrogenation process, which facilitates the mobility of active hydrogen and therefore promotes the intrinsic activity. More importantly, the ultrathin catalyst shows good reusability.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2017
·
IF 6.216
Wenjuan Shen,Bingning Wang,Falong Jia,Zhihui Ai,Lizhi Zhang
In general, the final product of atrazine (ATR) degradation by reactive oxygen species is cyanuric acid bearing a stable s -triazine ring, which is not further oxidized under mild conditions. In this study, we demonstrate that the presence of Ni(II) can increase the aerobic ATR degradation rate of core–shell Fe@Fe 2 O 3 nanowires (CSFN) by 6 times and also achieve the cleavage of recalcitrant s -triazine ring. The cleavage of s -triazine ring in this novel system was confirmed by the measurements of formic acid and nitrite acid. On the basis of experimental results, a feasible mechanism was proposed to account for the promoted aerobic ATR degradation and the facile s -triazine ring cleavage as follows. First, Ni(II) adsorbed on the surface of CSFN was reduced to nickel metal, which favored the generation of active hydrogen (•H). The in-situ generated •H then reduced ATR to 4-ethylamino-6-isopropylamino-1,3,5-triazine intermediate of easy ring opening property, rather than the recalcitrant cyanuric acid. Finally, this ATR degradation pathway change promoted the aerobic ATR degradation and benefited the s -triazine ring cleavage. This study clarifies the importance of degradation pathway on the ring-opening of organic pollutants, and also provides a mild method to remove s -triazine herbicides with molecular oxygen and zero-valent iron.
研究领域:
环境科学
·
化学
✓ 已验证
DOI
高影响因子
ACS Catalysis
·
2024
·
IF 11.3
Minghua Dong,Sen Luan,Yuxuan Wu,Bin Zhang,Ye Liu,Huizhen Liu,Buxing Han
Unveiling the mechanism behind catalyst-dependent solvent effects for hydrogenation reactions is critically important yet presents significant challenges. In this work, focusing on furfural hydrogenation over Pd-based catalysts, we observe that distinct active hydrogen species present on Pd/MgO and Pd/TiO2 exhibit different responses to solvation environments, consequently influencing the selectivity in diverse solvents. Product distribution over Pd/MgO remains unaffected by the solvents used that tetrahydrofurfural (THFAL) emerged as the primary product in both organic solvents and water. Conversely, product distribution over Pd/TiO2 highly depends on the solvents; THFAL dominates in organic solvents, whereas furfural alcohol (FOL) becomes the primary product in water. The disparate selectivity upon alteration of supports and solvents is demonstrated by neural network-enhanced molecular dynamics simulations and microkinetic modeling. The active hydrogen species on the support are stabilized in water by water-mediated charge reconstructions, facilitating the hydrogenation of C═O to produce FOL. A spillover pathway where hydrogen species transfer to supports directly without involving hydrogen bond networks is dynamically preferred in both water and organic solvents.
研究领域:
催化化学
·
理论计算化学
✓ 已验证
DOI
高影响因子
WATER RESEARCH
·
2025
·
IF 12.4
Hao Zhang,Xupeng Liu,Biao Zhou,Ziyue Chen,Jundi Cheng,Kehang Zeng,Lizhi Zhang,Hongwei Sun,Zhihui Ai
Mercury (Hg) is a toxic metal of great concern, and its reduction from Hg(II) to Hg(0) is crucial to prevent its mobilization and transformation to even more hazardous methylmercury. Fe° could reduce Hg(II), but the role of active hydrogen species (*H) remains unexplored. Herein, we prepared the phosphate-modified zero-valent iron by ball milling (P-ZVI bm ) and investigated its Hg(II) reduction and immobilization capacity compared with the ZVI bm counterpart. P-ZVI bm rapidly adsorbed and reduced Hg(II) from water at a rate 22 times faster than ZVI bm , with *H accounting for 36% of Hg(II) reduction. A greatly higher proportion of negative surface electrostatic potential on P-ZVI bm (50.38%) than ZVI bm (37.61%) facilitated the adsorption of Hg(II) cation. H 2 O adsorption on P-ZVI bm was more favorable, as demonstrated by the in situ ATR-FTIR spectra, H 2 O TPD-mass spectra, and the substantially lower adsorption energy (-0.78 eV) than ZVI bm (-0.17 eV). The energy span of H 2 O dissociation to *H also decreased from 2.80 eV on ZVI bm to 1.99 eV on P-ZVI bm . Moreover, *H adsorption energy on P-ZVI bm (1.70 eV) was lower than on ZVI bm (-1.20 eV), thereby inhibiting consumption of *H by H 2 evolution. P-ZVI bm demonstrated remarkable efficacy in removing Hg(II), Cu(II), Ni(II), Cd(II), and Pb(II) from electroplating and mining wastewater. These results highlight P-ZVI bm as a promising material for Hg(II) and other heavy metal remediation and underscore the essential role of *H in the enhanced Hg(II) reduction.
研究领域:
环境科学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ChemCatChem
·
2024
·
IF 3.8
Jinlian Liu,Liang Jiang,Bo Xing,Fuping Zhang,Yi Wang,Qilong Zhao,Mingliang Wu,Xin Chen,Guo Yang
Graphical The Pd/ZrO 2 catalyst prepared by the impregnation reduction method showed excellent activity and selectivity in the synthesis of HMTHF via the selective hydrogenation of the furan ring in 5-HMF at ambient hydrogen pressure and room temperature. Furthermore, the influence of the type of active hydrogen species on the hydrogenation of furan rings was proved by hydrogen spillover experiments. 5-Hydroxymethylfurfural (5-HMF) derived from lignocellulose represents an important platform molecule that could be employed in the selective hydrogenation of the furan ring to prepare 5‑hydroxymethyltetrahydrofurfural (HMTHF). However, the reported catalytic systems for the synthesis of HMTHF using 5-HMF still require additional hydrogen pressure. In this study, the Pd/ZrO 2 catalyst with uniformly dispersed Pd nanoparticles was prepared via a simple impregnation reduction process. This catalyst exhibited excellent catalytic activity and selectivity for the hydrogenation of 5-HMF to HMTHF. High HMTHF yields up to 92.3% were produced under mild reaction conditions of ambient hydrogen pressure and room temperature in methanol solvent. This result was superior to the most catalytic systems that had been reported so far. The mechanism study revealed that the active hydrogen species on the surface of the Pd nanoparticles and the reaction solvent in this study were the pivotal factors influencing the hydrogenation of furan rings in 5-HMF.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Energy Materials
·
2024
·
IF 5.4
Heng Chen,Li Li,Shichao Zhang,Chaofeng Zhang
Recently, as an important product of the CO2 hydrogenation reaction and a crucial hydrogen storage material, the transformation of formic acid (FA)/formate to H2 or active hydrogen species has attracted much attention. However, obtaining a robust and efficient solid catalyst constitutes a major challenge. In this work, nitrobenzene was used as the active hydrogen species capture agent, and various Pd-based catalysts were prepared and used to refine the influence factors of FA decomposition over TiO2-supported palladium catalysts. The catalysts’ deactivation and regeneration process, control reactions, and catalyst characterizations indicate that the electrical state of the Pd species and interface microsurroundings played decisive roles in the activity and reusability of PdO/TiO2. Based on the results obtained, a tentative mechanism with the active sites (Pdδ+–O–Ti) located at the PdO/TiO2 interface was proposed, which would be useful for the chemistry of the Pd catalyst and formate decomposition.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2023
·
IF 7.4
Guang-Hui Liu,Yong-Chao Qi,Han Wang,Ai-Min Wang,Yu-Hong Kang,Yong Gao,Ni Bai,Zhan-Ku Li,Xian-Yong Wei
This paper focused on the complementary advantages of density functional theory (DFT) calculation and catalytic reaction regulation. Based on the effective identification of intermediates, the possible catalytic hydroconversion (CHC) pathways of lignite-derived aryl ethers over Ni/mordenite were discussed. Bond dissociation energy (BDE) calculations of >C–O– bonds in different substrates and intermediates show that BDEs of >C ar –O– bonds are generally higher than those of >C al –O– bonds, and there is obvious electron aggregation near O atoms. Mulliken charge distribution analyses of different atomic sites further revealed the possible adsorption sites of active hydrogen, especially H · and H + . Possible cleavage pathways were further speculated by evaluating the stability of different leaving groups. In the early stage of CHC, aromatic ring hydrogenation and >C al –O– bond cleavage dominate, rather than >C ar –O– bond cleavage. Enthalpy change analyses combined with the CHC of real substrates further indicate that lowering temperature is beneficial to the cleavage of >C ar –O– bonds under the premise of inhibiting H ··· H transfer and obtaining H · effectively. Appropriately increasing the support acidity to ensure sufficient H + release is conducive to >C al –O– bond cleavage, especially direct dehydroxylation/dehydration. The analysis of synergetic transfer pathways of active hydrogen during the CHC provides theoretical guidance for the pathway optimization of converting lignite into high-quality clean liquid fuels.
研究领域:
化学工程
·
能源科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Nano
·
2025
·
IF 16
Xing Sun,Yanzheng He,Mengfan Wang,Qiyang Cheng,Yunfei Huan,Sisi Liu,Jie Liu,Tao Qian,Chenglin Yan,Jianmei Lu
Electrochemical nitrate reduction reaction (NO3RR) stands out as a promising route for sustainable ammonia synthesis, in which active hydrogen (*H) plays a crucial role in both the deoxygenation and hydrogenation steps. However, the regulation of surface *H is still overlooked, and without intervention, the competing hydrogen evolution reaction is kinetically more favored over the NO3RR, leaving the current system as far from satisfactory. Herein, based on reverse utilization of the Sabatier principle, a series of FexNiy substitutional solid-solution alloys (SSAs) are synthesized to manipulate *H behavior for enhanced NO3RR. Upon precise optimization of the alloy composition, the d-band center of HER-active Ni shifts toward the Fermi level, endowing the catalyst with strong interaction to *H and greatly prolonging its lifetime, which enables abundant supply to facilitate the NO3RR. As expected, a maximum NH3 yield rate of 31.46 mmol h–1 mg–1 is delivered over the optimized Fe3Ni1–SSA, which is considerably higher than most of the extensively reported works. Several in situ characterizations are combined to gain in-depth insight. Especially, in situ Fourier transform infrared spectroscopy in internal reflection mode directly observes *H enrichment on the catalyst surface, while the accompanied facilitation of the NO3RR process is verified by external reflection mode.
研究领域:
材料科学
·
化学工程
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Sustainable Materials and Technologies
·
2024
·
IF 8.6
Yijun Chen,Meina Cheng,Hailiang Yang,Sanjian Ma,Long Jin,Zixia Lin,Xin Liu
The traditional Fenton process has two issues that hinder its further application and promotion. One is the generation of large amounts of iron sludge. The other is the safe storage and transport of explosive H 2 O 2 . The problems could be solved by accelerating to regenerate Fe(II) and realizing to self-generate H 2 O 2 . The key to the solution lies in the use of reducing active hydrogen [H] to supply electrons. The effect of different loading methods of Pd 0 nanoparticles (NPs), active centres for [H] generation, on the catalytic performance is unknown. Herein, the Pd/UiO-66(Zr) (Pd 0 NPs loaded on the surface of UiO-66(Zr)) and Pd@UiO-66(Zr) (Pd 0 NPs confined into the pores of UiO-66(Zr)) were synthesized. It confirmed that the [H] could be used to promote to regenerate Fe(II) and self-generate H 2 O 2 . Using only a trace amount of ferrous (25 μM) and without H 2 O 2 , the trimethoprim (20 mg·L −1 ) could be thoroughly removed within 90 min. Moreover, the stability of Pd@UiO-66(Zr) was slightly superior to that of Pd/UiO-66(Zr) because of the confinement effect of pore wall on Pd 0 NPs, as well as the interception effect on the intermediate products that can be complexed with Pd 0 NPs.
研究领域:
环境科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）