List of Issues

Chinese Journal of Catalysis
2023, Vol. 44
Online: 18 January 2023

Previous Issue    Next Issue

Cover: Prof. Yantao Shi and coworkers in their article on pages 117–126 reported an unusual light-driven CO₂ assimilation (into methanol) by the PSII core complex in photosynthesis. The extraordinary finding is likely to be a simultaneous event along with the usual electron transfer occurring in normal light-independent assimilation

For Selected:

Download Citations EndNote Ris BibTeX

Toggle Thumbnails

Highlights

Select

A macro library for monatomic catalysts Jingyi Han, Jingqi Guan 2023, 44:  1-3.  DOI: 10.1016/S1872-2067(22)64153-6 Abstract ( 333 )   HTML ( 40 )   PDF (1152KB) ( 361 )

Select

Solar to H2O2 in-situ generation and utilization: A self-cyclable photocatalytic Fenton-like system Peng Zhang, Youji Li, Xin Li 2023, 44:  4-6.  DOI: 10.1016/S1872-2067(22)64185-8 Abstract ( 164 )   HTML ( 16 )   PDF (10010KB) ( 131 )

Reviews

Select

Recent progress on design and applications of transition metal chalcogenide-associated electrocatalysts for the overall water splitting Hui Su, Jing Jiang, Shaojia Song, Bohan An, Ning Li, Yangqin Gao, Lei Ge 2023, 44:  7-49.  DOI: 10.1016/S1872-2067(22)64149-4 Abstract ( 523 )   HTML ( 52 )   PDF (23310KB) ( 502 )   Electrochemical hydrogen evolution via water splitting has been regarded as a highly promising technique for fossil-fuel substitution in the future to avoid environmental pollution and energy waste. As half of the water splitting reaction, the oxygen evolution reaction (OER) is the major obstacle because of the sluggish kinetics of the complex reaction. It is imperative and urgent to develop highly efficient, low cost and earth-abundant electrocatalysts to overcome the sluggish kinetics issue. Among the various non-noble-metal-based electrocatalysts, transition metal chalcogenide (TMS) associated materials have been exploited as potential candidates for the past few years due to their excellent electrochemical performance and unique internal structure. In this review, we have summarized the recent advances of transition metal sulfides (TMSs) for hydrogen evolution reaction (HER), OER, and overall water splitting, then we have reviewed several modified strategies from the perspective of their functional concepts to synthesis methods, characterization techniques, catalytic mechanisms and performances. Finally, the existing deficiencies, challenges and future development directions of TMSs in OER, HER, and overall water splitting process are further discussed and summarized.

Select

Excluding false positives: A perspective toward credible ammonia quantification in nitrogen reduction reaction Ya Li, Zhenkang Wang, Haoqing Ji, Lifang Zhang, Tao Qian, Chenglin Yan, Jianmei Lu 2023, 44:  50-66.  DOI: 10.1016/S1872-2067(22)64148-2 Abstract ( 146 )   HTML ( 15 )   PDF (4291KB) ( 248 )   As an essential raw material for fertilizer production and promising green fuels, ammonia is significant to the national economy and social development. Recently, nitrogen reduction reaction (NRR) towards ammonia under mild conditions has received intensive attention due to environmental friendliness and low energy consumption, compared to the rigorous and contaminative Haber-Bosch process. However, as current research deepens, some fatal challenges emerged in this field‒not only high volatility and low repeatability but false‒positive results, casting serious doubts about its prospects. In this review, we summarized and discussed some potential factors that possibly induce false-positive results for accurate ammonia quantification, including the aspects of catalyst materials, experimental process, and quantification methods. And corresponding methods to eliminate these effects are also summarized. Furthermore, a promising protocol and several control principles are proposed to eliminate potential errors during ammonia quantification. This review establishes a paradigm base in NRR research field toward more accurate ammonia quantification.

Select

Indium-based ternary metal sulfide for photocatalytic CO2 reduction application Jinman Yang, Zhengrui Yang, Kefen Yang, Qing Yu, Xingwang Zhu, Hui Xu, Huaming Li 2023, 44:  67-95.  DOI: 10.1016/S1872-2067(22)64152-4 Abstract ( 301 )   HTML ( 16 )   PDF (10528KB) ( 286 )   Photocatalytic CO2 reduction technology appears one of the most prospective paths because it directly utilizes green and renewable solar energy to efficiently convert CO2 into hydrocarbon fuels and useful chemical products, which will dissipate global warming and mitigate universal problems of energy shortage simultaneously. Metal sulfide based on appropriate band structures and excellent photoresponsivity range has recently attracted attention in the basic research of CO2 photoconversion in laboratory. In particular, In-based ternary metal sulfide present great potential in dealing with photo corrosion and carrier recombination problems. This review detailedly introduced the main structural characteristics and common synthesis methods of In-based ternary metal sulfide. Additionally, a series of modification methods of In-based ternary metal sulfide and recent developments of activity enhancing techniques in photocatalytic CO2 conversion were summarized and analyzed as the central content. Subsequently, we systematically demonstrated and discussed the mechanism of activity enhancement. Finally, we highlighted the current limitations, challenges and development needs and directions of In-based ternary metal sulfide for photocatalytic CO2 conversion.

Select

Molecule-electron-proton transfer in enzyme-photo-coupled catalytic system Shihao Li, Jiafu Shi, Shusong Liu, Wenping Li, Yu Chen, Huiting Shan, Yuqing Cheng, Hong Wu, Zhongyi Jiang 2023, 44:  96-110.  DOI: 10.1016/S1872-2067(22)64154-8 Abstract ( 369 )   HTML ( 19 )   PDF (27308KB) ( 372 )   Supporting Information Enzyme-Photo-coupled Catalytic System (EPCS) integrates the light absorption capacity of photocatalysts and the high activity/specificity of enzymes, which is becoming an emerging technology platform to mimic natural photosynthesis for harnessing solar energy to generate valuable products, including bulk chemicals, energy chemicals and pharmaceutical chemicals. Cofactors including NAD(P)+/NAD(P)H, as "energy currency", are involved in over 80% biocatalytic redox reactions, establishing a bridge of mass/energy exchange between photocatalysis and cofactor-dependent enzyme catalysis. Although numerous efforts have been devoted, the performance of current EPCS is far from the theoretical upper limit. The individual and synergistic intensification of molecule-electron-proton transfer evolves a critical yet challenging issue in EPCS. This Review will focus on the molecule-electron-proton transfer in natural photosynthesis and in EPCS. Future endeavors to intensify all three transfers to construct a more efficient EPCS are suggested as pursuit for a new pattern of modern chemical engineering.

Communication

Select

Visible light-induced Z-scheme V2O5/g-C3N4 heterojunction catalyzed cascade reaction of unactivated alkenes Qing-Wen Gui, Fan Teng, Peng Yu, Yi-Fan Wu, Zhi-Bin Nong, Long-Xi Yang, Xiang Chen, Tian-Bao Yang, Wei-Min He 2023, 44:  111-116.  DOI: 10.1016/S1872-2067(22)64162-7 Abstract ( 128 )   HTML ( 9 )   PDF (895KB) ( 223 )   Supporting Information The Z-scheme V2O5/g-C3N4 heterojunction was firstly applied in heterogeneous visible light-induced cascade reaction for constructing phosphoryled ring-fused quinazolinones. Both the photogenerated hole and photogenerated electron played a vital role in the radical cascade process.

Articles

Select

Light-driven CO2 assimilation by photosystem II and its relation to photosynthesis Yuehui Li, Duanhui Si, Wangyin Wang, Song Xue, Wenzhe Shang, Zhanyou Chi, Can Li, Ce Hao, Govindjee Govindjee, Yantao Shi 2023, 44:  117-126.  DOI: 10.1016/S1872-2067(22)64170-6 Abstract ( 99 )   HTML ( 19 )   PDF (1630KB) ( 287 )   Supporting Information For natural oxygenic photosynthesis, there is a consensus that H2O is oxidized to molecular oxygen by photosystem II (PSII) in the grana, while CO2 assimilation takes place, long after oxygen evolution, in light-independent reactions, for example, through the Calvin-Benson Cycle in the stroma. Here, we report, for the first time, light-driven CO2 assimilation by the PSII core complex, where the formation of methanol, along with the oxygen evolution, is validated by in-situ mass spectrometry, gas chromatography and isotopic labeling experiments. Such an unusual CO2 assimilation is likely to be a simultaneous event along with the usual electron transfer occurring in normal light-independent assimilation. This discovery is extraordinary and is of great significance as it may substantially modify our understanding of the mechanism of photosynthesis.

Select

Investigation of nickel iron layered double hydroxide for water oxidation in different pH electrolytes Qixian Xie, Dan Ren, Lichen Bai, Rile Ge, Wenhui Zhou, Lu Bai, Wei Xie, Junhu Wang, Michael Grätzel, Jingshan Luo 2023, 44:  127-138.  DOI: 10.1016/S1872-2067(22)64190-1 Abstract ( 411 )   HTML ( 23 )   PDF (2806KB) ( 341 )   Supporting Information Nickel iron layered double hydroxide (NiFe LDH) is one of the best oxygen evolution reaction (OER) catalysts in alkaline electrolytes. However, it performs poorly in neutral electrolytes, and the detailed mechanism is still unclear. Herein, we introduce electrochemical measurements, operando surface enhanced Raman spectroscopy and operando 57Fe Mössbauer spectroscopy to elucidate the mechanism of NiFe LDH for OER process in different pH electrolytes. Our results show that even though there exist Ni3+ and Fe4+ species, the NiFe LDH based electrocatalysts still show worse OER performance in neutral electrolytes than in alkaline conditions. Combining the electrochemical measurements with spectroscopic investigations, we demonstrated that the rate-determining step (RDS) of OER on NiFe LDH based electrocatalysts is from *O to *OOH in alkaline medium while *OH formation is the RDS in neutral conditions. Our work provides new insights into elucidating the OER mechanism in different pH electrolytes.

Select

Enzyme-metal-single-atom hybrid catalysts for one-pot chemoenzymatic reactions Xiaoyang Li, Yufei Cao, Jiarong Xiong, Jun Li, Hai Xiao, Xinyang Li, Qingqiang Gou, Jun Ge 2023, 44:  139-145.  DOI: 10.1016/S1872-2067(22)64179-2 Abstract ( 164 )   HTML ( 8 )   PDF (1645KB) ( 235 )   Supporting Information Combining enzymatic and single-metal-atom catalysis is a promising approach for green chemical synthesis. We herein report a one-pot chemoenzymatic cascade reaction to asymmetric synthesize (R)-1-(4-biphenyl) ethanol by using the highly active and selective enzyme-metal-single-atom hybrid as the catalyst. We demonstrate that the Pd single atoms anchored lipase (Pd1/CALB-P) can efficiently drive one-pot cascade reactions in aqueous solution at 30 °C to achieve facile synthesis of chiral biaryl alcohols, which are important pharmaceutical intermediates that traditionally require complex synthesis procedures. The rate of (R)-1-(4-biphenyl) ethanol formation catalyzed by Pd1/CALB-P is more than 30-fold higher than that of the combination of commercial palladium on carbon (Pd/C) and lipase-pluronic conjugate (CALB-P). The enzyme-metal-single-atom hybrid catalyst provides a promising strategy for effectively merging the enzymatic and single-atom catalysis.

Select

Inter-plane 2D/2D ultrathin La2Ti2O7/Ti3C2 MXene Schottky heterojunctions toward high-efficiency photocatalytic CO2 reduction Ke Wang, Miao Cheng, Nan Wang, Qianyi Zhang, Yi Liu, Junwei Liang, Jie Guan, Maochang Liu, Jiancheng Zhou, Naixu Li 2023, 44:  146-159.  DOI: 10.1016/S1872-2067(22)64155-X Abstract ( 168 )   HTML ( 14 )   PDF (20578KB) ( 255 )   Supporting Information Ascribing to incremental fossil fuels emissions, the utilization and conversion of CO2 and development of renewable energy is globally essential and significative. Ultrathin 2D/2D heterojunctions with fast photo-generated electrons transmission channels illustrate a better strategy to improve photocatalytic activity. Herein, combing La2Ti2O7 with metallic few-layered Ti3C2 MXene to construct inter-plane 2D/2D heterojunction was in situ self-assembled through solvothermal method. Benefiting from the advantages including stability, conductivity, abundant active sites and formation of Schottky junctions, as expected, the ultrathin 2D/2D La2Ti2O7/Ti3C2 MXene nanosheets presented much improved photocatalytic ability for CO2 reduction to CO and CH4, which is about 4.6 and 11.4 times higher than that of mechanical mixed La2Ti2O7 and Ti3C2 MXene. fs-TAS and XPS provided direct evidence that the prominence of La2Ti2O7/Ti3C2 MXene in photocatalytic CO2 reduction reaction over other opponents should be attributed to the synergetic effect of efficient charge carrier mobility and formed 2D/2D Schottky heterojunction interfacial contact between La2Ti2O7 and Ti3C2 MXene. Intermediates revealed by in-situ DRIFTS and corresponding atomic-level DFT calculations confirmed the mechanism, pathways and selectivity for photocatalytic CO2 conversion. This work expanded promising prospects arouses new impetus for deepening the prehension of the mechanism of photocatalytic CO2 reduction, designing and fabrication of Schottky heterojunctions for application in conversion and utilization of CO2.

Select

A photodecarboxylase from Micractinium conductrix active on medium and short-chain fatty acids Yunjian Ma, Xuanru Zhong, Bin Wu, Dongming Lan, Hao Zhang, Frank Hollmann, Yonghua Wang 2023, 44:  160-170.  DOI: 10.1016/S1872-2067(22)64173-1 Abstract ( 133 )   HTML ( 10 )   PDF (6561KB) ( 170 )   Hydrocarbons are essential base chemicals as energy carriers and starting materials for chemical manufacture. So-called fatty acid photodecarboxylases (FAPs) represent interesting catalysts for the conversion of natural fatty acids into hydrocarbons thereby giving access to alkanes from renewable feedstock. Today, however, only few FAPs are known. In the current study we report a new FAP from the marine organism Micractinium conductrix (McFAP). In contrast to currently known FAPs McFAP exhibits high catalytic activity towards short and medium fatty acids. Recombinant expression and basic biochemical characterisation of this new member of the FAP family is reported.

Select

Biocatalytic aminohydroxylation of styrenes for efficient synthesis of enantiopure β-amino alcohols Ruiwen Hu, Anjie Gong, Langxing Liao, Yan-Xin Zheng, Xin Liu, Peng Wu, Fushuai Li, Huili Yu, Jing Zhao, Long-Wu Ye, Binju Wang, Aitao Li 2023, 44:  171-178.  DOI: 10.1016/S1872-2067(22)64174-3 Abstract ( 125 )   HTML ( 11 )   PDF (1250KB) ( 192 )   Supporting Information A general biocatalytic process of intermolecular aminohydroxylation of styrenes with aniline has been achieved for efficient one-pot preparation of enantiopure β-amino alcohols. The reaction involves first asymmetric epoxidation of alkene substrates by a heme-dependent monooxygenase (P450) or the FAD-dependent styrene monooxygenase, followed by the aminolysis of nascent epoxide intermediates with aniline in water solution. Hybrid cluster-continuum (HCC) model calculations reveal the mechanism of the aminolysis of epoxide with aniline as well as the critical role of the water in mediating such a reaction. In addition, the combined experiments with simulations demonstrate that the chirality of amino alcohol is determined by the absolute configuration of the epoxide formed in the enzymatic reaction. In conclusion, the developed biocatalytic process provides an efficient, environmentally friendly approach for production of high value-added enantiopure β-amino alcohols, starting from cheap and readily available alkenes.